Photosensitive coloring composition, cured product, coloring spacer and image display device
阅读说明：本技术 感光性着色组合物、固化物、着色间隔物及图像显示装置 (Photosensitive coloring composition, cured product, coloring spacer and image display device ) 是由 泽井良尚 裴丽华 伊藤敦哉 大津猛 于 2018-06-29 设计创作，主要内容包括：本发明提供能够形成可抑制波长400～500nm的漏光、机械特性优异的着色间隔物的感光性着色组合物、着色间隔物、以及具备这样的着色间隔物的图像显示装置。本发明的感光性着色组合物的一个方式为,其含有：(a)着色剂、(b)碱可溶性树脂、(c)光聚合引发剂、及(d)烯属不饱和化合物,其中,在感光性着色组合物的全部固体成分中,所述(a)着色剂的含有比例为23质量％以下,所述(a)着色剂包含橙色颜料,且所述(a)着色剂中的所述橙色颜料的含有比例为45质量％以上。(The invention provides a photosensitive coloring composition capable of forming a coloring spacer which can inhibit light leakage with the wavelength of 400-500 nm and has excellent mechanical characteristics, the coloring spacer and an image display device with the coloring spacer. One embodiment of the photosensitive coloring composition of the present invention is a photosensitive coloring composition comprising: (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound, wherein the content of the colorant (a) is 23 mass% or less, the colorant (a) contains an orange pigment, and the content of the orange pigment in the colorant (a) is 45 mass% or more, based on the total solid content of the photosensitive coloring composition.)
1. A photosensitive coloring composition, comprising: (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound,
the content of the colorant (a) is 23% by mass or less in the entire solid content of the photosensitive coloring composition,
the (a) colorant comprises an orange pigment, and,
the content ratio of the orange pigment in the colorant (a) is 45 mass% or more.
2. The photosensitive coloring composition according to claim 1, wherein the orange pigment comprises at least one selected from the group consisting of c.i. pigment orange 13, c.i. pigment orange 43, c.i. pigment orange 64, and c.i. pigment orange 72.
3. The photosensitive coloring composition according to claim 1 or 2, wherein a content ratio of the blue pigment and the violet pigment in the colorant (a) is 50% by mass or less.
4. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the (a) colorant further comprises a yellow pigment.
5. The photosensitive coloring composition according to claim 4, wherein the yellow pigment comprises at least one selected from the group consisting of C.I. pigment yellow 138, C.I. pigment yellow 139, and C.I. pigment yellow 150.
6. The photosensitive coloring composition according to any one of claims 1 to 5, wherein the content of the colorant (a) is 1% by mass or more in the entire solid content of the photosensitive coloring composition.
7. The photosensitive coloring composition according to any one of claims 1 to 6, which is used for forming a coloring spacer.
8. A photosensitive coloring composition, comprising: (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound,
the photosensitive coloring composition is used for forming a coloring spacer,
the content ratio of the colorant (a) is 23 mass% or less in the entire solid content of the photosensitive coloring composition,
the chromaticity coordinate (x, y) of the photosensitive coloring composition in an xy chromaticity diagram satisfies 0.40-0.55 x and 0.35-0.50 y.
9. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 8.
10. A colored spacer comprising the cured product according to claim 9.
11. An image display device provided with the colored spacer according to claim 10.
Technical Field
The present invention relates to a photosensitive coloring composition and the like. More specifically, the present invention relates to a photosensitive coloring composition preferably used for forming a color spacer or the like in a color filter of a liquid crystal display or the like, a cured product obtained by curing the photosensitive coloring composition, a color spacer, and an image display device provided with the color spacer.
The entire contents of the specification, claims, drawings and abstract of Japanese patent application 2017-129366, which was filed by the patent office on the day 6/30 of 2017, and the entire contents of documents cited in the specification and the like are incorporated herein as the disclosure of the present specification.
Background
A Liquid Crystal Display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by on/off of a voltage applied to the liquid crystal. On the other hand, each member constituting a cell of a liquid crystal display is often formed by a method using a photosensitive composition typified by photolithography. The photosensitive composition is expected to be applied in a wide range in the future because of its ease of forming a fine structure and the ease of processing a large-area substrate.
In addition, in view of the features of high resolution, low cost, and thin profile, the backlight used in the liquid crystal display is currently widely used in the mobile terminal and television industry as an LED backlight.
Recently, in order to cope with further higher definition and higher luminance of a color liquid crystal display, an active matrix type liquid crystal display has been proposed, in which a color filter having a color filter provided on a TFT element substrate side is integrated into an array substrate (COA type), and a black matrix having only a black matrix provided on the TFT element substrate side is integrated into an array substrate (BOA type). In this method, as compared with the case where a black matrix is formed on the color filter side, it is not necessary to provide a margin (margin) for alignment with the active element side, and therefore the aperture ratio can be increased, and as a result, high luminance can be achieved. Such a black matrix structure is required to have high light-shielding properties and to suppress light leakage in a visible light region as much as possible.
In addition, as the structure and manufacturing process of the liquid crystal display become simpler, a colored spacer in which a so-called column spacer, a photo spacer and a black matrix are integrated has been developed for keeping the interval between 2 substrates in the liquid crystal display constant. As such a colored spacer, a colored spacer using a plurality of organic colored pigments as pigments has been proposed (see, for example,
On the other hand, as in patent documents 3 to 5, there has been proposed a liquid crystal display device in which 1 or 2 or more color filter layers are provided on the opposing portions of the colored spacers of the frame portion.
Disclosure of Invention
Problems to be solved by the invention
The present inventors have studied and found that, in various panel structures, particularly in a liquid crystal display including an LED backlight, in a structure in which a blue color filter layer is provided in a portion of a frame portion opposite to a color spacer, a blue light component from an LED is easily transmitted, and light leakage at a wavelength of 400 to 500nm is often generated in the color spacer formed using the photosensitive color composition described in
In addition, since the step of press-bonding the substrate having the color spacers and the counter substrate is performed in the manufacturing of the liquid crystal display, the color spacers need to have mechanical properties such as elastic recovery that the color spacers return to their original shape when the external pressure is released even if the color spacers are deformed by the external pressure in the press-bonding step.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a photosensitive colored composition capable of forming a colored spacer which can suppress light leakage at a wavelength of 400 to 500nm and has excellent mechanical properties.
Means for solving the problems
As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific pigment as a colorant, setting the content ratio of the pigment to a specific range, and setting the content ratio of the colorant to a specific range, and have completed the present invention.
That is, the present invention has the following configurations [1] to [11 ].
[1] A photosensitive coloring composition, comprising: (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound,
the content of the colorant (a) is 23% by mass or less in the entire solid content of the photosensitive coloring composition,
the (a) colorant comprises an orange pigment, and,
the content ratio of the orange pigment in the colorant (a) is 45 mass% or more.
[2] The photosensitive coloring composition according to [1], wherein the orange pigment comprises at least one selected from the group consisting of c.i. pigment orange 13, c.i. pigment orange 43, c.i. pigment orange 64, and c.i. pigment orange 72.
[3] The photosensitive coloring composition according to [1] or [2], wherein a content ratio of the blue pigment and the violet pigment in the colorant (a) is 50% by mass or less.
[4] The photosensitive coloring composition according to any one of the above [1] to [3], wherein the colorant (a) further contains a yellow pigment.
[5] The photosensitive coloring composition according to [4], wherein the yellow pigment comprises at least one selected from the group consisting of C.I. pigment yellow 138, C.I. pigment yellow 139 and C.I. pigment yellow 150.
[6] The photosensitive coloring composition according to any one of the above [1] to [5], wherein the content ratio of the colorant (a) is 1% by mass or more in the entire solid content of the photosensitive coloring composition.
[7] The photosensitive colored composition according to any one of the above [1] to [6], which is used for forming a colored spacer.
[8] A photosensitive coloring composition, comprising: (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound,
the photosensitive coloring composition is used for forming a coloring spacer,
the content ratio of the colorant (a) is 23 mass% or less in the entire solid content of the photosensitive coloring composition,
the chromaticity coordinate (x, y) of the photosensitive coloring composition in an xy chromaticity diagram satisfies 0.40-0.55 x and 0.35-0.50 y.
[9] A cured product obtained by curing the photosensitive coloring composition according to any one of the above [1] to [8 ].
[10] A colored spacer comprising the cured product according to [9 ].
[11] An image display device comprising the colored spacer according to [10 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a photosensitive colored composition, a cured product, a colored spacer, and an image display device provided with such a colored spacer, which are capable of forming a colored spacer having excellent mechanical properties and capable of suppressing light leakage at a wavelength of 400 to 500nm, can be provided.
Drawings
Fig. 1 shows an emission spectrum of a light source used for chromaticity measurement and color tone evaluation.
Detailed Description
The present invention is not limited to the following embodiments, and can be carried out with various modifications within the scope of the gist thereof.
In the present invention, "(meth) acryl" means "acryl and/or methacryl", "(meth) acrylate" and "(meth) acryl" are also the same.
The meaning of the "(co) polymer" includes both homopolymer (homopolymer) and copolymer (copolymer), and the meaning of the "acid (anhydride)", "… acid (anhydride)" includes both acid and anhydride thereof. In the present invention, the "acrylic resin" refers to a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylate having a carboxyl group.
In the present invention, the term "monomer" is a term that is opposite to a so-called high molecular substance (polymer), and includes a dimer, a trimer, an oligomer, and the like in addition to a monomer (monomer) in a narrow sense.
In the present invention, the "total solid content" refers to all components other than the solvent contained in the photosensitive coloring composition or the ink described later.
In the present invention, "weight average molecular weight" means a weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) and converted to polystyrene.
In the present invention, unless otherwise specified, the "amine number" represents an amine number converted into an effective solid content, and is a value expressed by the equivalent KOH mass as an amount of base per 1g of solid content of the dispersant. The measurement method will be described later. On the other hand, unless otherwise specified, the "acid value" means an acid value converted into an effective solid content, and is calculated by neutralization titration.
In the present specification, the percentage and the part by mass are the same as the percentage and the part by weight.
In the present specification, a specific example of a pigment may be indicated by a pigment number, and terms such as "c.i. pigment red 2" refer to a pigment reference number (c.i.).
[ photosensitive coloring composition ]
The photosensitive coloring composition of the invention contains the following components as essential components:
(a) coloring agent
(b) Alkali soluble resin
(c) Photopolymerization initiator
(d) Ethylenically unsaturated compounds
If necessary, the composition further contains other compounding ingredients such as an adhesion improver such as a silane coupling agent, a surfactant (coatability improver), a pigment derivative, a photoacid generator, a crosslinking agent, a mercapto compound, a development modifier, an ultraviolet absorber, and an antioxidant, and each compounding ingredient is usually used in a state of being dissolved or dispersed in a solvent.
In the photosensitive coloring composition according to
On the other hand, the photosensitive coloring composition of embodiment 2 of the present invention is a photosensitive coloring composition for forming a coloring spacer, wherein the content ratio of the colorant (a) is 23% by mass or less in the entire solid content of the photosensitive coloring composition, and chromaticity coordinates (x, y) of the photosensitive coloring composition in an xy chromaticity diagram satisfy 0.40. ltoreq. x.ltoreq.0.55 and 0.35. ltoreq. y.ltoreq.0.50.
Hereinafter, unless otherwise specified, "photosensitive colored composition of the present invention" refers to both the photosensitive colored composition of
< (a) a colorant
The colorant (a) contained in the photosensitive coloring composition of the present invention is a component for coloring the photosensitive coloring composition. By containing the colorant (a), desired light absorption characteristics can be obtained. As the colorant (a), a pigment or a dye may be used.
In the photosensitive coloring composition of the invention of
Examples of orange pigments (orange pigments) include:
(a) The content of the orange pigment in the colorant may be 45% by mass or more, and is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass, from the viewpoint of greatly suppressing the transmittance at a wavelength of 400 to 500 nm.
On the other hand, from the viewpoint of broadening the absorption wavelength band by utilizing the optical characteristics of the colorant other than the orange pigment, it is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, and particularly preferably 80% by mass or less. The combination of the upper limit and the lower limit is, for example, preferably 45 to 95% by mass, more preferably 50 to 90% by mass, still more preferably 60 to 85% by mass, and particularly preferably 70 to 80% by mass.
(a) The colorant may contain a colorant other than an orange pigment (hereinafter, simply referred to as "other colorant"). Examples of the other colorant include pigments and dyes, and pigments are preferable from the viewpoint of heat resistance, and organic pigments are preferable from the viewpoint of color tone, photocurability, and sensitivity.
Examples of the pigment include organic coloring pigments such as yellow pigment, red pigment, blue pigment, violet pigment, green pigment, and brown pigment.
Examples of the yellow pigment include: c.i. pigment yellow 1, 1:1, 2,3,4,5,6, 9, 10, 12, 13, 14,16, 17, 24, 31, 32, 34, 35:1, 36:1, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62: 1. 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127: 1. 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191: 1. 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. Among them, c.i. pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 are preferable from the viewpoint of dispersibility and reliability, c.i. pigment yellow 138, 139, 150 is more preferable, and c.i. pigment yellow 139 is particularly preferable from the viewpoint of light-shielding property.
Examples of the red pigment include: c.i.
Examples of the blue pigment include: pigment blue 1, 1:2, 9, 14, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56:1, 60, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Among them, from the viewpoint of light-shielding properties, c.i. pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, and 60 are preferable, and c.i. pigment blue 15:6 and 16 are more preferable.
In addition, c.i. pigment blue 15:6, 16, and 60 is preferably used from the viewpoint of dispersibility and light-shielding properties, and when the photosensitive coloring composition is cured by ultraviolet light, a pigment having a low ultraviolet absorption rate is preferably used as the blue pigment, and from this viewpoint, c.i. pigment blue 60 is more preferably used. On the other hand, as described in korean patent laid-open No. 10-1840984, c.i. pigment blue 16 is preferably used from the viewpoint of reliability, light-shielding properties, and elastic recovery.
Examples of the violet pigment include: c.i.
On the other hand, c.i. pigment violet 29 is preferably used from the viewpoint of dispersibility.
Examples of the green pigment include: c.i.
Examples of brown pigments (brown pigments) include: c.i. pigment brown 23, 25, 26, 28, 38, 41, 83, 93. Among them, c.i. pigment brown 26, 28, 83, 93 is preferable from the viewpoint of having both near infrared light transmittance and light-shielding property.
Among these organic coloring pigments, a yellow pigment or a red pigment is preferable, and a yellow pigment is more preferable, since the pigment has an absorption band in the vicinity of a wavelength of 400 to 500 nm.
When the yellow pigment is contained, the content of the yellow pigment in the colorant (a) is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 20% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, and particularly preferably 30% by mass or less. When the lower limit value is not less than the above-mentioned lower limit value, the transmittance at a wavelength of 400 to 500nm tends to be low, and when the upper limit value is not more than the above-mentioned upper limit value, the Optical Density (OD) tends to be high. The combination of the upper limit and the lower limit is, for example, preferably 1 to 50% by mass, more preferably 5 to 50% by mass, still more preferably 10 to 40% by mass, yet more preferably 20 to 35% by mass, and particularly preferably 20 to 30% by mass.
When the colorant (a) contains a red pigment, the content of the red pigment in the colorant (a) is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and particularly preferably 10% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably 15% by mass or less. When the lower limit value is not less than the above-mentioned lower limit value, the Optical Density (OD) tends to be high, and when the upper limit value is not more than the above-mentioned upper limit value, the transmittance at a wavelength of 400 to 500nm tends to be low. The combination of the upper limit and the lower limit is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, still more preferably 5 to 20% by mass, yet more preferably 5 to 15% by mass, and particularly preferably 10 to 15% by mass.
From the viewpoint of color tone, organic coloring pigments other than the yellow pigment and the red pigment, for example, blue pigment and violet pigment, are preferably contained at a low ratio. From this viewpoint, the total content of the blue pigment and the violet pigment in the colorant (a) is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, particularly preferably 20% by mass or less, and most preferably 0% by mass. That is, it is most preferable that the colorant (a) does not contain a blue pigment or a violet pigment.
(a) The content of the blue pigment in the colorant is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, particularly preferably 20% by mass or less, and most preferably 0% by mass. When the amount is equal to or less than the upper limit, a favorable color tone tends to be formed.
(a) The content of the violet pigment in the colorant is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, particularly preferably 20% by mass or less, and most preferably 0% by mass. When the amount is equal to or less than the upper limit, a favorable color tone tends to be formed.
On the other hand, from the viewpoint of light-shielding properties, a blue pigment and/or a violet pigment may be contained. In this case, the total content ratio of the blue pigment and the violet pigment in the colorant (a) is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and particularly preferably 10% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably 15% by mass or less. When the lower limit value is not less than the above-mentioned lower limit value, the Optical Density (OD) tends to be high, and when the upper limit value is not more than the above-mentioned upper limit value, the transmittance at a wavelength of 400 to 500nm tends to be low. The combination of the upper limit and the lower limit is, for example, preferably 2 to 50 mass%, more preferably 5 to 40 mass%, still more preferably 8 to 30 mass%, still more preferably 10 to 20 mass%, and particularly preferably 10 to 15 mass%.
In addition, as another colorant, a black pigment may be contained. Examples of the black pigment include an organic black pigment and an inorganic black pigment. Examples of the organic black pigment include organic black pigments containing at least one selected from the group consisting of a compound represented by the following formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound.
[ chemical formula 1]
In the formula (1), R 1And R 6Each independently is a hydrogen atom, CH 3、CF 3Fluorine atom or chlorine atom;
R 2、R 3、R 4、R 5、R 7、R 8、R 9and R 10Each independently is a hydrogen atom, a halogen atom, R 11、COOH、COOR 11、COO -、CONH 2、CONHR 11、CONR 11R 12、CN、OH、OR 11、COCR 11、OOCNH 2、OOCNHR 11、OOCNR 11R 12、NO 2、NH 2、NHR 11、NR 11R 12、NHCOR 12、NR 11COR 12、N＝CH 2、N＝CHR 11、N＝CR 11R 12、SH、SR 11、SOR 11、SO 2R 11、SO 3R 11、SO 3H、SO 3 -、SO 2NH 2、SO 2NHR 11Or SO 2NR 11R 12；
And is selected from R 2And R 3、R 3And R 4、R 4And R 5、R 7And R 8、R 8And R 9And R 9And R 10Optionally bonded directly to each other, or through an oxygen atom, a sulfur atom, NH or NR 21Bridging to bond each other;
R 11and R 12Each independently is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms.
The geometric isomer of the compound represented by the general formula (1) has the following core structure (in which a substituent in the structural formula is omitted), and the trans-trans isomer may be the most stable.
[ chemical formula 2]
When the compound represented by the general formula (1) is anionic, it is preferably a salt obtained by compensating the charge of any known suitable cation, for example, a metal, organic, inorganic or metal organic cation, specifically a tertiary amine such as an alkali metal, an alkaline earth metal, a transition metal, a primary amine, a secondary amine or a trialkylamine, or a quaternary ammonium or organometallic complex compound such as tetraalkylammonium. When the geometric isomer of the compound represented by the general formula (1) is anionic, the same salt is preferable.
Among the substituents of the general formula (1) and their definitions, the following substituents are preferred from the viewpoint of having a tendency to increase the shielding rate. This is because the following substituents are not absorbed and do not affect the hue of the pigment.
R 2、R 4、R 5、R 7、R 9And R 10Each independently is preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.
R 3And R 8Each independently preferably represents a hydrogen atom or NO 2、OCH 3、OC 2H 5Bromine atom, chlorine atom, CH 3、C 2H 5、N(CH 3) 2、N(CH 3)(C 2H 5)、N(C 2H 5) 2α -naphthyl, β -naphthyl, SO 3H or SO 3 -More preferably a hydrogen atom or SO 3H。
R 1And R 6Each independently preferably represents a hydrogen atom or CH 3Or CF 3More preferably a hydrogen atom.
Preferably selected from R 1And R 6、R 2And R 7、R 3And R 8、R 4And R 9And R 5And R 10Is the same, more preferably R 1And R 6Same, R 2And R 7Same, R 3And R 8Same, R 4And R 9Are identical and R 5And R 10The same is true.
Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a 2-methylbutyl group, an n-pentyl group, a 2-pentyl group, a 3-pentyl group, a2, 2-dimethylpropyl group, an n-hexyl group, a heptyl group, an n-octyl group, a1, 1,3, 3-tetramethylbutyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, and.
Cycloalkyl having 3 to 12 carbon atoms is, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, thujyl, norbornyl, norcarane, carane-yl, methyl-ethyl, methyl-propyl, methyl-,
Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1, 3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl and 2- The radical-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1, 4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl or dodecenyl.
Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2, 4-cyclohexadien-1-yl and 1-p-cyclonen En-8-yl, 4(10) -limonene-10-yl, 2-norbornen-1-yl, 2, 5-norbornadien-1-yl, 7-dimethyl-2, 4-norcareen-3-yl, or camphyl.
Examples of the alkynyl group having 2 to 12 carbon atoms include a 1-propyn-3-yl group, a 1-butyn-4-yl group, a 1-pentyn-5-yl group, a 2-methyl-3-butyn-2-yl group, a1, 4-pentadiyn-3-yl group, a1, 3-pentadiyn-5-yl group and a 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1, 3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl or 1-dodecyn-12-yl.
The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The organic black pigment is preferably a compound represented by the following general formula (2) and/or a geometric isomer of the compound, and more preferably a compound represented by the following general formula (2).
[ chemical formula 3]
Specific examples of such an organic Black pigment include those sold under the trade name Irgaphor (registered trademark) Black S0100 CF (manufactured by BASF corporation).
The organic black pigment is preferably used after being dispersed by a dispersant, a solvent or a method described later. Further, if a sulfonic acid derivative of the compound represented by the above general formula (1) or a sulfonic acid derivative of a geometric isomer of the above compound, particularly a sulfonic acid derivative of the compound represented by the above general formula (2) or a sulfonic acid derivative of a geometric isomer of the above compound is present at the time of dispersion, the dispersibility and the storage stability may be improved.
In addition, as the organic black pigment, from the viewpoint of optical characteristics and reliability, it is preferable to use an organic black pigment described in Korean laid-open patent No. 10-2018-0052502 and an organic black pigment described in Korean laid-open patent No. 10-2018-0052864.
Further, as other organic black pigments, aniline black, xeronine black, perylene black, and the like can be given. In addition, carbon black, which is an inorganic black pigment, may also be used. Examples of the carbon black include the following.
Mitsubishi chemical corporation: MA7, MA8, MA11, MA77, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #2650, #3030, # 30550, #3250, #3400, #3600, #3750, #3950, #4000, #4010, # 7B, OIL9B, OIL11B, OIL30B, OIL31B, and # 263033
Manufactured by Degussa: printex (registered trademark, the same below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Special Black550, Special Black350, Special Black250, Special Black100, Special Black6, Special Black5, Special Black4, Color FW1, Color FW2, Color Black 2V, Color Black 18, Color Black 200, Black S160, Color FW 170S 170
Manufactured by Cabot corporation: monarch (registered trademark, the same below) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, the same below) 99, REGAL99R, REGAL415R, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACKPEELARLS 480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark) -8
Manufactured by Birla corporation: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
Carbon black coated with a resin may be used as the carbon black. When carbon black coated with a resin is used, the adhesion to a glass substrate and the volume resistance value are improved. As the carbon black coated with a resin, for example, carbon black described in japanese patent application laid-open No. h 09-71733 can be preferably used. In view of volume resistance and dielectric constant, resin-coated carbon black is preferably used.
These pigments are preferably used by being dispersed so that the average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the average particle diameter is based on the number of pigment particles.
In the photosensitive coloring composition, the average particle diameter of the pigment is a value determined from the particle diameter of the pigment measured by Dynamic Light Scattering (DLS). The particle size measurement is performed on the photosensitive coloring composition after being sufficiently diluted (usually diluted to prepare a pigment concentration of about 0.005 to 0.2 mass%, but according to the recommended concentration of the pigment by a measuring instrument), and the measurement is performed at 25 ℃.
In addition, as other coloring agents, dyes other than the above pigments may be used. Examples of the dye that can be used as another colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinonimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
As azo dyes, there may be mentioned, for example: c.i. acid yellow 11, c.i. acid orange 7, c.i. acid red 37, c.i. acid red 180, c.i. acid blue 29, c.i. direct red 28, c.i. direct red 83, c.i. direct yellow 12, c.i. direct orange 26, c.i. direct green 28, c.i. direct green 59, c.i. active yellow 2, c.i. active red 17, c.i. active red 120, c.i. active black5, c.i. disperse orange 5, c.i. disperse red 58, c.i. disperse blue 165, c.i. basic blue 41, c.i. basic red 18, c.i. medium red 7, c.i. medium yellow 5, c.i. medium black 7, etc.
Examples of the anthraquinone-based dye include: c.i. vat blue 4, c.i. acid blue 40, c.i. acid green 25, c.i. active blue 19, c.i. active blue 49, c.i. disperse red 60, c.i. disperse blue 56, c.i. disperse blue 60, etc.
Examples of the phthalocyanine dyes include c.i. vat blue 5, quinonimine dyes include c.i. basic blue 3 and c.i. basic blue 9, quinoline dyes include c.i. solvent yellow 33, c.i. acid yellow 3 and c.i. disperse yellow 64, and examples of the nitro dyes include c.i. acid yellow 1, c.i. acid orange 3 and c.i. disperse yellow 42.
On the other hand, in the photosensitive coloring composition of the invention of embodiment 2, the colorant (a) is not particularly limited as long as it is a colorant or a combination of colorants capable of forming a photosensitive coloring composition in which chromaticity coordinates (x, y) in an xy chromaticity diagram described later satisfy 0.40. ltoreq. x.ltoreq.0.55 and 0.35. ltoreq. y.ltoreq.0.50.
For example, the colorant (a) may be a red pigment and a yellow pigment, and the content ratio thereof is adjusted so that the chromaticity coordinates (x, y) satisfy the above range. In addition, there can be mentioned: a combination of red and yellow pigments and violet pigments, a combination of brown and yellow pigments and violet pigments, a combination of orange and yellow pigments, a combination of orange and red pigments, a combination of orange and yellow pigments and red pigments, a combination of orange and violet pigments, a combination of orange and blue pigments and a combination of orange and violet pigments. In addition, those listed in
Specific examples of the pigment species having chromaticity coordinates (x, y) satisfying the above-mentioned range and the content ratio thereof, and the values of the chromaticity coordinates (x, y) in each specific example are shown in table 1. The content ratio of the pigment in the table is a value in the entire solid content of the photosensitive coloring composition.
[ Table 1]
The abbreviations in table 1 are as follows.
Y139: c.i. pigment yellow 139
R254: c.i. pigment red 254
Br 41: c.i. pigment brown 41
Alkali soluble resin (b)
The alkali-soluble resin (b) used in the present invention is not particularly limited as long as it contains a carboxyl group or a hydroxyl group, and examples thereof include: epoxy (meth) acrylate resins, acrylic resins, carboxyl group-containing epoxy resins, carboxyl group-containing urethane resins, novolak resins, polyvinyl phenol resins, and the like, and among them, from the viewpoint of excellent platemaking properties, it is preferable to use:
(b1) epoxy (meth) acrylate resin
(b2) An acrylic resin, a resin containing a vinyl group,
these may be used singly or in combination.
< (b1) epoxy (meth) acrylate resin
(b1) The epoxy (meth) acrylate resin is obtained by further reacting a polybasic acid and/or an anhydride thereof with a hydroxyl group formed by a reaction product of an epoxy resin (epoxy compound) and α -unsaturated monocarboxylic acid and/or α -unsaturated monocarboxylic acid ester having a carboxyl group.
Further, the (b1) epoxy (meth) acrylate resin is also included in the (b1) epoxy (meth) acrylate resin, which is obtained by reacting a compound having 2 or more substituents capable of reacting with a hydroxyl group before reacting the hydroxyl group with the polybasic acid and/or the anhydride thereof, and then reacting the compound with the polybasic acid and/or the anhydride thereof.
Further, a resin obtained by further reacting a compound having a reactive functional group with a carboxyl group of the resin obtained by the above reaction is also included in the above (b1) epoxy (meth) acrylate resin.
Therefore, epoxy (meth) acrylate resins are not limited to "(meth) acrylate" because they have substantially no epoxy group in their chemical structure, but they are conventionally named because epoxy compounds (epoxy resins) are used as raw materials and "(meth) acrylate" is a typical example thereof.
As the (b1) epoxy (meth) acrylate resin used in the present invention, the following epoxy (meth) acrylate resin (b1-1) and/or epoxy (meth) acrylate resin (b1-2) (hereinafter, may be referred to as "carboxyl group-containing epoxy (meth) acrylate resin") is particularly preferably used from the viewpoint of developability and reliability.
< epoxy (meth) acrylate resin (b1-1) >
An alkali-soluble resin obtained by adding α -unsaturated monocarboxylic acid and/or α -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin and then reacting the resulting product with a polybasic acid and/or an acid anhydride thereof.
< epoxy (meth) acrylate resin (b1-2) >
An alkali-soluble resin obtained by adding α -unsaturated monocarboxylic acid and/or α -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin and then reacting the resulting product with a polyhydric alcohol and a polybasic acid and/or an acid anhydride thereof.
Here, the epoxy resin is a material including a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins and used. In addition, as the epoxy resin, a compound obtained by reacting a phenol compound with epichlorohydrin may be used. The phenol compound is preferably a compound having a phenolic hydroxyl group having a valence of 2 or more, and may be a monomer or a polymer.
As the kind of the raw material epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, triphenol methane type epoxy resin, biphenol novolac type epoxy resin, naphthalene novolac type epoxy resin, epoxy resin which is a reaction product of addition polymerization reaction of dicyclopentadiene and phenol or cresol and further reaction with epichlorohydrin, adamantyl group-containing epoxy resin, fluorene type epoxy resin, etc. can be preferably used, and epoxy resin having an aromatic ring in the main chain in this way can be suitably used.
Specific examples of the epoxy resin include, for example, bisphenol A type epoxy resins (for example, "jER (registered trademark, the same shall apply hereinafter)" 828 "," jER-1001 "," jER-1002 "," jER-1004 ", and the like manufactured by Mitsubishi chemical corporation)," NER-1302 "(epoxy equivalent 323, softening point 76 ℃ and the like manufactured by Nippon Kabushiki Kaisha), bisphenol F type resins (for example," jER-807 "," jER-4004P "," jER-4005P "," jER-4007P ", and" NER-7406 "(epoxy equivalent 350, softening point 66 ℃ and the like manufactured by Mitsubishi chemical corporation), bisphenol S type epoxy resins, biphenyl glycidyl ethers (for example," jER-YX-4000 ", manufactured by Mitsubishi chemical corporation), phenol novolac type epoxy resins (for example," EPPN-201 ", manufactured by Nippon Kabushiki Kaisha, "jER-152", "jER-154" manufactured by mitsubishi chemical corporation, "DEN-438" manufactured by Dow chemical corporation), ("o-, m-, and P-) cresol novolak-type epoxy resins (for example," EOCN (registered trademark, the same below) "102S", "EOCN-1020", "EOCN-104S" manufactured by mitsubishi chemical corporation), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by nippon chemical corporation), triphenol methane-type epoxy resins (for example, "EPPN (registered trademark, the same below)" 501 "," EPN-502 "," EPPN-503 "manufactured by mitsubishi chemical corporation), alicyclic epoxy resins (for example," Celloxide (registered trademark, the same below) "2021P", "Celloxide", and epoxy resins obtained by glycidating phenolic resins produced by reacting dicyclopentadiene with phenol (for example, "EXA-7200" manufactured by DIC, and "NC-7300" manufactured by Nippon Kabushiki Kaisha), epoxy resins represented by the following general formulae (B1) to (B4), and the like. Specifically, there may be mentioned "XD-1000" manufactured by Nippon Kabushiki Kaisha as an epoxy resin represented by the following general formula (B1), "NC-3000" manufactured by Nippon Kabushiki Kaisha as an epoxy resin represented by the following general formula (B2), "ESF-300" manufactured by Nippon Kabushiki Kaisha as an epoxy resin represented by the following general formula (B4), and the like.
[ chemical formula 4]
In the general formula (B1), a represents an average value and represents a number of 0 to 10, and R 111Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. In addition, a plurality of R present in 1 molecule 111May be the same or different.
[ chemical formula 5]
In the general formula (B2), B represents an average value and represents a number of 0 to 10, and R 121Represents a hydrogen atom, a halogen atom, a carbon atom1 to 8 alkyl groups, cycloalkyl groups having 3 to 10 carbon atoms, phenyl groups, naphthyl groups or biphenyl groups. In addition, a plurality of R present in 1 molecule 121May be the same or different.
[ chemical formula 6]
In the general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2), and c represents an integer of 2 or 3. Wherein the molecular structure contains more than 1 adamantane structure.
[ chemical formula 7]
In the above general formulae (B3-1) and (B3-2), R 131～R 134And R 135～R 137Each independently represents an adamantyl group optionally having a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms optionally having a substituent, or a phenyl group optionally having a substituent, and ＊ represents a bonding position.
[ chemical formula 8]
In the general formula (B4), p and q each independently represent an integer of 0 to 4, and R 141And R 142Each independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, R 143And R 144Each independently represents an alkylene group having 1 to 4 carbon atoms, and x and y each independently represent an integer of 0 or more.
Among these, epoxy resins represented by any of general formulae (B1) to (B4) are preferably used.
Examples of α -unsaturated monocarboxylic acid or α -unsaturated monocarboxylic acid ester having a carboxyl group include monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-or p-vinylbenzoic acid, and a halogenated alkyl group at position α of (meth) acrylic acid, an alkoxy group, a halogen atom, a nitro group, and a cyano group-substituted compound, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylsalic adipic acid, 2- (meth) acryloyloxyethylsalic phthalic acid, 2- (meth) acryloyloxyethylsalic maleic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- (meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutylacryladipic acid, 2- (meth) acryloyloxybutylphthalic acid anhydride, 2- (meth) acrylobutylic acid, pentaerythritol (di (meth) acryloxy) acrylic anhydride, pentaerythritol (α -butyl) acrylate, pentaerythritol (γ) acrylate, and the like.
Among these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.
As the method for adding α -unsaturated monocarboxylic acid and/or α -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used, for example, α -unsaturated monocarboxylic acid and/or α -unsaturated monocarboxylic acid ester having a carboxyl group can be reacted with an epoxy resin at a temperature of 50 to 150 ℃ in the presence of an esterification catalyst.
The epoxy resin, the α -unsaturated monocarboxylic acid and/or the α -unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used singly or in combination of 2 or more.
α -unsaturated monocarboxylic acid and/or β 0, β 1-unsaturated monocarboxylic acid ester having a carboxyl group are used in an amount preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents, based on 1 equivalent of an epoxy group in an epoxy resin, and by setting the amount of α -unsaturated monocarboxylic acid and/or α -unsaturated monocarboxylic acid ester having a carboxyl group to the lower limit or more, there is a tendency that the amount of introduction of an unsaturated group can be suppressed and the subsequent reaction with a polybasic acid and/or an acid anhydride thereof becomes sufficient, and on the other hand, by setting the amount to the upper limit or less, there is a tendency that the unreacted product of α -unsaturated monocarboxylic acid and/or α -unsaturated monocarboxylic acid ester having a carboxyl group can be suppressed from remaining and curing properties can be easily improved.
Examples of the polybasic acid and/or the acid anhydride thereof include one or 2 or more selected from the group consisting of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthalate, endomethylenetetrahydrophthalic acid, hexachloronorbornene diacid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and acid anhydrides of these acids.
Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid or anhydrides of these acids are preferred. Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride or biphenyltetracarboxylic dianhydride.
The addition amount of the polybasic acid and/or the acid anhydride component thereof is preferably in the range of 10 to 150mg KOH/g, more preferably in the range of 20 to 140mg KOH/g, the addition amount of the polybasic acid and/or the acid anhydride component thereof is preferably not less than the lower limit, whereby alkali developability tends to be good, and the addition amount of the polybasic acid and/or the acid anhydride component thereof is not more than the upper limit, whereby curability tends to be good.
In addition reaction of the polybasic acid and/or the acid anhydride thereof, a polyhydric alcohol such as trimethylolpropane, pentaerythritol, dipentaerythritol, or the like may be added to introduce a multi-branched structure.
The carboxyl group-containing epoxy (meth) acrylate resin is generally obtained by heating after mixing the polybasic acid and/or its anhydride with the reactant of the epoxy resin with α -unsaturated monocarboxylic acid and/or β 0, β 1-unsaturated monocarboxylic acid ester having a carboxyl group, or after mixing the polybasic acid and/or its anhydride and the polyhydric alcohol with the reactant of the epoxy resin with α -unsaturated monocarboxylic acid and/or α -unsaturated monocarboxylic acid ester having a carboxyl group, in which case the mixing order of the polybasic acid and/or its anhydride and the polyhydric alcohol is not particularly limited, by heating, the addition reaction of the polybasic acid and/or its anhydride and any hydroxyl group present in the mixture of the reactant of the epoxy resin with α -unsaturated monocarboxylic acid and/or α -unsaturated monocarboxylic acid ester having a carboxyl group and the polyhydric alcohol is carried out.
As the carboxyl group-containing epoxy (meth) acrylate resin, in addition to the above, carboxyl group-containing epoxy (meth) acrylate resins described in Korean laid-open patent No. 10-2013-0022955, Korean granted patent No. 10-0965189, Japanese patent laid-open publication No. 2005-165294, and Japanese patent laid-open publication No. 2006-312704 can be mentioned.
The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin in terms of polystyrene, as measured by Gel Permeation Chromatography (GPC), is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, and further preferably 2500 or more, and is usually 10000 or less, preferably 8000 or less, more preferably 6000 or less, further preferably 5000 or less, and particularly preferably 4000 or less. When the lower limit value is set to be equal to or higher than the lower limit value, the solubility in the developer tends to be suppressed from becoming excessively high, and when the upper limit value is set to be equal to or lower than the upper limit value, the solubility in the developer tends to be easily improved. For example, the combination of the upper limit and the lower limit is, for example, preferably 1000 to 10000, more preferably 1500 to 8000, further preferably 2000 to 6000, further preferably 2500 to 5000, and particularly preferably 2500 to 4000.
The acid value of the epoxy (meth) acrylate resin is not particularly limited, and is preferably 10mgKOH/g or more, more preferably 20mgKOH/g or more, and is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, further preferably 100mgKOH/g or less, and particularly preferably 50mgKOH/g or less. When the lower limit value is not less than the above lower limit value, appropriate developing solubility tends to be obtained, and when the upper limit value is not more than the above upper limit value, film dissolution tends to be suppressed without excessive development. The combination of the upper limit and the lower limit is, for example, preferably 10 to 200mg KOH/g, more preferably 10 to 150mg KOH/g, still more preferably 10 to 100mg KOH/g, and particularly preferably 20 to 50mg KOH/g.
The chemical structure of the epoxy (meth) acrylate resin (b1) is not particularly limited, and examples thereof include an epoxy (meth) acrylate resin (b1-a) having a partial structure (1) represented by the following general formula (I) (hereinafter, may be simply referred to as "epoxy (meth) acrylate resin (b 1-a)"). Since the epoxy (meth) acrylate resin (b1-a) has 3 or more (meth) acryloyloxy groups in the partial structure represented by the formula (I), the amount of ethylenic double bonds in 1-molecule resin is large, and when a colored spacer is formed using a photosensitive colored composition containing the resin, the crosslinking density becomes high, elution of impurities into a solvent is suppressed, high reliability can be ensured, and the mechanical properties tend to be improved because the crosslinking density of the spacer becomes high.
(partial structure (1))
[ chemical formula 9]
In the above formula (I), R 1Represents a hydrogen atom or a methyl group;
R 2、R 3、R 5and R 6Each independently represents optionally having a substituentAlkylene of a substituent;
R 4a linking group representing a valence of n + 1;
R 7represents an alkylene group optionally having a substituent, an alkenylene group optionally having a substituent, or an aromatic ring group optionally having a substituent;
l and m each independently represent an integer of 0 to 12;
n represents an integer of 3 or more;
denotes the bonding site.
(R 2、R 3、R 5And R 6)
In the above formula (I), R 2、R 3、R 5And R 6Each independently represents an alkylene group optionally having a substituent.
The alkylene group may be linear, branched, or cyclic, or a combination thereof. The number of carbon atoms is not particularly limited, and is usually 1 or more, and is usually 8 or less, preferably 6 or less, more preferably 4 or less, and further preferably 2 or less. When the content is not more than the above upper limit, the compatibility with other components tends to be good.
Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and a cyclohexylene group, and from the viewpoint of compatibility with other components, a methylene group or an ethylene group is preferable, and a methylene group is more preferable.
Examples of the substituent optionally contained in the alkylene group include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, a carboxyl group and the like, and the substituent is preferably unsubstituted from the viewpoint of ease of synthesis.
(R 4)
In the above general formula (I), R 4Represents a linking group having a valence of n + 1. The chemical structure of the n + 1-valent linking group is not particularly limited, and an n + 1-valent hydrocarbon group optionally having a substituent may be mentioned. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group from the viewpoint of developability. Further, the carbon-carbon single bond in the hydrocarbon group may be interrupted by at least 1 selected from the group consisting of-O-, -CO-and-NH-.
Specific examples of the n + 1-valent linking group include the following groups, and in the chemical formula, a x represents a bonding position.
[ chemical formula 10]
(R 7)
In the above formula (I), R 7Represents an alkylene group optionally having a substituent, an alkenylene group optionally having a substituent, or a 2-valent aromatic ring group optionally having a substituent.
R 7The alkylene group in (b) may be linear, branched or cyclic, or a combination thereof. The number of carbon atoms is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less, and more preferably 4 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Specific examples of the alkylene group include: methylene, ethylene, propylene, hexylene, cyclohexylene, and the like, and methylene or ethylene is preferred, and ethylene is more preferred, from the viewpoint of curability.
Examples of the substituent optionally contained in the alkylene group include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group, and the substituent is preferably unsubstituted from the viewpoint of curability.
R 7The alkenylene group in (b) may be linear, branched or cyclic, or a combination thereof. The number of carbon atoms is not particularly limited, but is usually 2 or more, preferably 4 or more, and usually 8 or less, preferably 6 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Specific examples of alkenylene groups include: vinylene, propenylene, butenylene, cyclohexenylene, and the like, and from the viewpoint of curability, vinylene or cyclohexenylene is preferred, and vinylene is more preferred.
Examples of the substituent optionally contained in the alkenylene group include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group, and the substituent is preferably unsubstituted from the viewpoint of curability.
As R 7As the 2-valent aromatic ring group in (A), a 2-valent aromatic ring group and a 2-valent aromatic heterocyclic group are mentioned. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, further preferably 15 or less, and particularly preferably 10 or less. When the amount is not less than the lower limit, the development adhesion tends to be good, and when the amount is not more than the upper limit, the curability tends to be good.
The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the 2-valent aromatic hydrocarbon ring group, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, perylene,
The aromatic heterocyclic ring in the 2-valent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the 2-valent aromatic heterocyclic group include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole rings having 2 free valences,
Among the aromatic ring groups having a valence of 2, a benzene ring or a naphthalene ring having a valence of 2 is preferable, and a benzene ring having a valence of 2 is more preferable, from the viewpoint of photocurability.
Examples of the substituent optionally contained in the 2-valent aromatic ring group include an alkyl group, an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.
Among these, R is R from the viewpoint of curability 7Preferred is an alkylene group optionally having a substituent, more preferred is an unsubstituted alkylene group, and further preferred is an ethylene group.
(l and m)
In the general formula (I), l and m each independently represent an integer of 0 to 12. From the viewpoint of development adhesion, it is preferably 0 or more, more preferably 1 or more, and from the viewpoint of curability, it is preferably 8 or less, more preferably 6 or less, further preferably 4 or less, and particularly preferably 2 or less. On the other hand, from the viewpoint of curability, 0 is preferable.
(n)
In the general formula (I), n represents an integer of 3 or more. n is preferably 4 or more, more preferably 5 or more, and preferably 10 or less, more preferably 8 or less, further preferably 7 or less, and particularly preferably 6 or less. When the lower limit value is not less than the above-mentioned lower limit value, curability tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, developing solubility tends to be good. The combination of the upper limit and the lower limit is, for example, preferably 4 to 10, more preferably 4 to 8, still more preferably 4 to 7, and particularly preferably 4 to 6.
(partial structure (2))
The epoxy (meth) acrylate resin (b1-a) preferably has a partial structure (2) represented by the following general formula (II) from the viewpoint of developing solubility.
[ chemical formula 11]
In the above formula (II), R 8Represents an alkylene group optionally having a substituent, an alkenylene group optionally having a substituent, or an aromatic ring group optionally having a substituent;
denotes the bonding site.
(R 8)
In the above formula (II), R 8Represents an alkylene group optionally having a substituent, an alkenylene group optionally having a substituent, or a 2-valent aromatic ring group optionally having a substituent.
R 8The alkylene group in (b) may be linear, branched or cyclic, or a combination thereof. The number of carbon atoms is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a hexylene group, and a cyclohexylene group, and from the viewpoint of curability, the alkylene group is preferably a methylene group or an ethylene group, and more preferably an ethylene group.
Examples of the substituent optionally contained in the alkylene group include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group, and the substituent is preferably unsubstituted from the viewpoint of curability.
R 8The alkenylene group in (b) may be linear, branched or cyclic, or a combination thereof. The number of carbon atoms is not particularly limited, but is usually 2 or more, preferably 4 or more, and usually 8 or less, preferably 6 or less. By the steps ofWhen the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Specific examples of alkenylene groups include: vinylene, propenylene, butenylene, cyclohexenylene, and the like, and from the viewpoint of curability, vinylene or cyclohexenylene is preferred, and vinylene is more preferred.
Examples of the substituent optionally contained in the alkenylene group include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group, and the substituent is preferably unsubstituted from the viewpoint of curability.
As R 8As the 2-valent aromatic ring group in (A), a 2-valent aromatic ring group and a 2-valent aromatic heterocyclic group are mentioned. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, further preferably 15 or less, and particularly preferably 10 or less. When the amount is not less than the lower limit, the development adhesion tends to be good, and when the amount is not more than the upper limit, the curability tends to be good.
The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the 2-valent aromatic hydrocarbon ring group, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, perylene,
The aromatic heterocyclic ring in the 2-valent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the 2-valent aromatic heterocyclic group include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole rings having 2 free valences,
Examples of the substituent optionally contained in the 2-valent aromatic ring group include an alkyl group, an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.
Among these, R is R from the viewpoint of curability 8Preferred is an optionally substituted alkenylene group, more preferred is an unsubstituted alkenylene group, and still more preferred is a cyclohexenylene group.
Specific examples of the partial structure (2) represented by the above formula (II) include the following partial structures, and a symbol in the chemical formula represents a bonding site.
[ chemical formula 12]
(partial structure (3))
The epoxy (meth) acrylate resin (b1-a) preferably has a partial structure (3) represented by the following general formula (III) from the viewpoint of curability.
[ chemical formula 13]
In the above formula (III), R 9Represents an epoxy resin residue, p represents an integer of 1 or more, and represents a bonding site.
(R 9)
In the above formula (III), R 9Represents an epoxy resin residue. The epoxy resin residue refers to a residue obtained by removing an epoxy group from an epoxy resin.
Here, the epoxy resin has the same meaning as described above.
(p)
In the formula (III), p represents an integer of 1 or more. From the viewpoint of having both curability and developing solubility, p is preferably 2. On the other hand, p is preferably 2 or more, more preferably 5 or more, and further preferably 10 or more from the viewpoint of curability, and is preferably 20 or less, more preferably 15 or less, and further preferably 12 or less from the viewpoint of development solubility. When the lower limit value is not less than the above-mentioned lower limit value, curability tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, developing solubility tends to be good.
(partial structure (3-1))
The partial structure (3) represented by the above formula (III) is preferably the partial structure (3-1) represented by the following formula (III-1) from the viewpoint of developing solubility.
[ chemical formula 14]
In the formula (III-1), γ represents a 2-valent linking group, and x represents a bonding position. The benzene ring in the formula (III-1) may be further substituted with an optional substituent.
(γ)
In the formula (III-1), γ represents a linking group having a valence of 2. The linking group having a valence of 2 may, from the viewpoint of developing solubility, be a single bond, or an optionally substituted alkylene group, -CO-or-SO 2-。
The alkylene group may be linear, branched or cyclic, or a combination thereof. The number of carbon atoms is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Specific examples of the alkylene group include: methylene, ethylene, propylene, butylene, hexylene, cyclohexylene, heptylene, octylene, dodecylene, methylene or propylene is preferred, and propylene is more preferred, from the viewpoint of curability.
Examples of the substituent optionally contained in the alkylene group include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group, and the substituent is preferably unsubstituted from the viewpoint of curability.
When the substituent(s) is (are) present, the number thereof is not limited, and may be 1 or 2 or more.
In addition, methylene (-CH) in alkylene 2-) has 2 hydrogen atoms substituted with a substituent, the 2 substituents may be linked to each other to form a hydrocarbon ring. Specific examples of γ in this case include a group represented by the following formula (IV) and a group represented by the following formula (V). In the formula,. indicates a bonding site.
[ chemical formula 15]
Examples of the optional substituent optionally contained in the benzene ring in the formula (III-1) include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of the substituents is also not particularly limited, and may be 1 or 2 or more. When the benzene ring in the above formula (III-1) has a substituent, 2 benzene rings in the formula (III-1) may be linked to each other through the substituent.
Among these, γ is preferably an alkylene group optionally having a substituent, more preferably an unsubstituted alkylene group, and further preferably a propylene group, from the viewpoint of curability.
(partial structure (3-2))
The partial structure (3) represented by the above general formula (III) is preferably a partial structure (3-2) represented by the following general formula (III-2) from the viewpoint of curability.
[ chemical formula 16]
In the above formula (III-2), a represents a bonding site. The benzene ring in the above formula (III-2) may be further substituted with an optional substituent.
Examples of the optional substituent(s) which may be present on the benzene ring in the above formula (III-2) include a hydroxyl group, an alkyl group, and an alkoxy group. The number of the substituents is also not particularly limited, and may be 1 or 2 or more. Among these, from the viewpoint of development adhesion, an alkyl group is preferable, a cycloalkyl group is more preferable, and an adamantyl group is further preferable.
(partial structure (3-3))
The partial structure (3) represented by the above general formula (III) preferably contains the partial structure (3-3) represented by the following general formula (III-3) from the viewpoint of curability.
[ chemical formula 17]
In the above formula (III-3), R 10Represents a 2-valent hydrocarbon group optionally having a substituent, and represents a bonding position. The benzene ring in the formula (III-3) may be further substituted with an optional substituent.
(R 10)
In the above formula (III-3), R 10Represents a 2-valent hydrocarbon group optionally having a substituent.
As the 2-valent hydrocarbon group, there may be mentioned: a 2-valent aliphatic group, a 2-valent aromatic group, and a group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic groups are linked.
Examples of the 2-valent aliphatic group include straight-chain, branched-chain, and cyclic groups, and combinations thereof. Among these, a linear group is preferable from the viewpoint of developing solubility, and a cyclic 2-valent aliphatic group is preferable from the viewpoint of developing adhesion. The number of carbon atoms is 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. When the amount is not less than the lower limit, the development adhesion tends to be good, and when the amount is not more than the upper limit, the curability tends to be good.
Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-hexylene, n-heptylene, and the like. Among these, methylene is preferable from the viewpoint of curability.
Specific examples of the 2-valent branched aliphatic group include: the aforementioned 2-valent linear aliphatic group has a structure having a side chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or the like.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the amount is not less than the lower limit, the development adhesion tends to be good, and when the amount is not more than the upper limit, the curability tends to be good. Specific examples of the 2-valent cyclic aliphatic group include: a group obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborneol ring, or an adamantane ring. Among these groups, from the viewpoint of rigidity of the skeleton, a group obtained by removing 2 hydrogen atoms from the adamantane ring is preferable.
As the substituent optionally having the 2-valent aliphatic group, there can be mentioned: a hydroxyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
Examples of the 2-valent aromatic ring group include a 2-valent aromatic ring group and a 2-valent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the 2-valent aromatic hydrocarbon ring group, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, perylene,
The aromatic heterocyclic ring in the 2-valent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the 2-valent aromatic heterocyclic group include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole rings having 2 free valences,
Among these, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having 2 free valences is preferable, and a benzene ring having 2 free valences is more preferable.
Examples of the substituent optionally contained in the aromatic ring having a valence of 2 include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.
Examples of the group in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked include groups in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked.
The number of the 2-valent aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the above-mentioned lower limit value, curability tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
The number of the 2-valent aromatic ring groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the above-mentioned lower limit value, curability tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Specific examples of the group in which 1 or more aliphatic groups having a valence of 2 are linked to 1 or more aromatic groups having a valence of 2 include groups represented by the following formulae (III-3-A) to (III-3-E). Among these groups, from the viewpoint of developing solubility, a group represented by the following formula (III-3-A) is preferable. In the formula,. indicates a bonding site.
[ chemical formula 18]
As described above, the benzene ring in the formula (III-3) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of the substituents is also not particularly limited, and may be 1 or 2 or more.
Among these, from the viewpoint of curability, the resin is preferably unsubstituted.
(partial structure (3-4))
The partial structure (3) represented by the above formula (III) preferably contains a partial structure (3-4) represented by the following general formula (III-4) from the viewpoint of curability.
[ chemical formula 19]
In the formula (III-4), γ represents a linking group having a valence of 2, and x represents a bonding position. The benzene ring in the formula (III-4) may be further substituted with an optional substituent.
As γ in the above formula (III-4), those described as γ in the above formula (III-1) can be preferably employed.
As the optional substituent optionally contained in the benzene ring in the formula (III-4), those described as the optional substituent optionally contained in the benzene ring in the formula (III-1) can be preferably used.
Among the partial structures (3-1) to (3-4), the epoxy (meth) acrylate resin (b1-A) preferably has the partial structure (3-1) from the viewpoint of developing solubility.
As a specific production method of the epoxy (meth) acrylate resin (b1-A), the method described in Japanese patent application laid-open No. 2007-119718 can be employed.
In addition, as the epoxy (meth) acrylate resin, from the viewpoint of curability, an epoxy (meth) acrylate resin (B1-B) having a partial structure represented by the following general formula (i) (hereinafter, may be abbreviated as "epoxy (meth) acrylate resin (B1-B)") and an epoxy (meth) acrylate resin (B1-C) having a partial structure represented by the following general formula (ii) (hereinafter, may be abbreviated as "epoxy (meth) acrylate resin (B1-C)") are preferable. From the viewpoint of reliability, the epoxy (meth) acrylate resin (b1-C) is more preferable.
[ chemical formula 20]
In the formula (i), R aRepresents a hydrogen atom or a methyl group, R bRepresents a 2-valent hydrocarbon group optionally having a substituent, and represents a bonding position. The benzene ring in formula (i) may be further substituted with an optional substituent.
[ chemical formula 21]
In the formula (ii), R cEach independently represents a hydrogen atom or a methyl group, R dRepresents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and represents a bonding position.
(R b)
The above formulae (i), R bRepresents a 2-valent hydrocarbon group optionally having a substituent.
As the 2-valent hydrocarbon group, there may be mentioned: a 2-valent aliphatic group, a 2-valent aromatic group, and a group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic groups are linked.
Examples of the 2-valent aliphatic group include straight-chain, branched-chain, and cyclic groups, and combinations thereof. Among these, a linear group is preferable from the viewpoint of developing solubility, and a cyclic 2-valent aliphatic group is preferable from the viewpoint of developing adhesion. The number of carbon atoms is 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. When the amount is not less than the lower limit, the development adhesion tends to be good, and when the amount is not more than the upper limit, the curability tends to be good.
Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-hexylene, n-heptylene, and the like. Among these, methylene is preferable from the viewpoint of curability.
Specific examples of the 2-valent branched aliphatic group include: the aforementioned 2-valent linear aliphatic group has a structure having a side chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or the like.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the amount is not less than the lower limit, the development adhesion tends to be good, and when the amount is not more than the upper limit, the curability tends to be good. Specific examples of the 2-valent cyclic aliphatic group include: a group obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborneol ring, or an adamantane ring. Among these groups, from the viewpoint of rigidity of the skeleton, a group obtained by removing 2 hydrogen atoms from the adamantane ring is preferable.
As the substituent optionally having the 2-valent aliphatic group, there can be mentioned: a hydroxyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
Examples of the 2-valent aromatic ring group include a 2-valent aromatic ring group and a 2-valent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
As the aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group, there may be mentionedMonocyclic or condensed ring. As the 2-valent aromatic hydrocarbon ring group, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, perylene,
The aromatic heterocyclic ring in the 2-valent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the 2-valent aromatic heterocyclic group include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole rings having 2 free valences,
Examples of the substituent optionally contained in the aromatic ring having a valence of 2 include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.
Examples of the group in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked include groups in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked.
The number of the 2-valent aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
The number of the 2-valent aromatic ring groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the above-mentioned lower limit value, curability tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Specific examples of the group in which 1 or more aliphatic groups having a valence of 2 are linked to 1 or more aromatic groups having a valence of 2 include groups represented by the following formulae (i-A) to (i-E). Among these groups, from the viewpoint of developing solubility, a group represented by the following formula (i-a) is preferable. In the formula,. indicates a bonding site.
[ chemical formula 22]
As described above, the benzene ring in the formula (i) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of the substituents is also not particularly limited, and may be 1 or 2 or more.
Among these, from the viewpoint of curability, the resin is preferably unsubstituted.
The partial structure represented by the general formula (i) is preferably a partial structure represented by the following general formula (i-1) from the viewpoint of curability.
[ chemical formula 23]
In the formula (i-1), R aAnd R bR has the same meaning as in the above formula (i) XRepresents a hydrogen atom or a polybasic acid residue, and represents a bonding position. The benzene ring in the formula (i-1) may be further substituted with an optional substituent.
The polybasic acid residue refers to a 1-valent group obtained by removing 1 OH group from a polybasic acid or an anhydride thereof. The polybasic acid may be one or 2 or more selected from the group consisting of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethenyltetrahydrophthalic acid, hexachloronorbornene diacid, methyltetrahydrophthalic acid, and biphenyl tetracarboxylic acid.
Among these, from the viewpoint of patterning characteristics, the polybasic acid is preferably maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, or biphenyltetracarboxylic acid, and more preferably tetrahydrophthalic acid or biphenyltetracarboxylic acid.
The partial structure represented by the above formula (i-1) contained in 1 molecule of the epoxy (meth) acrylate resin (B1-B) may be 1 or 2 or more, and for example, R may be present in combination XIs a hydrogen atom and R XIs a polybasic acid residue.
The number of partial structures represented by the above formula (i) contained in 1 molecule of the epoxy (meth) acrylate resin (B1-B) is not particularly limited, and is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less. When the lower limit value is not less than the above-mentioned lower limit value, curability tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, developing solubility tends to be good.
Specific examples of the epoxy (meth) acrylate resin (B1-B) are shown below.
[ chemical formula 24]
[ chemical formula 25]
[ chemical formula 26]
[ chemical formula 27]
(R d)
In the above formula (ii), R dRepresents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less carbon atoms. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Specific examples of the alicyclic ring in the alicyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborneol ring, and an adamantane ring. Among these, an adamantane ring is preferable from the viewpoint of reliability.
On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and more preferably 3 or more, and is usually 10 or less, preferably 5 or less, and more preferably 4 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and particularly preferably 12 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,
In addition, the 2-valent hydrocarbon group in the 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include: a 2-valent aliphatic group, a 2-valent aromatic group, and a group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic groups are linked.
Examples of the 2-valent aliphatic group include straight-chain, branched-chain, and cyclic groups, and combinations thereof. Among these, a linear group is preferable from the viewpoint of compatibility, and a cyclic 2-valent aliphatic group is preferable from the viewpoint of reliability. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and further preferably 15 or less. When the amount is not less than the lower limit, the development adhesion tends to be good, and when the amount is not more than the upper limit, the curability tends to be good.
Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-hexylene, n-heptylene, and the like. Among these, methylene is preferable from the viewpoint of curability.
Specific examples of the 2-valent branched aliphatic group include: the aforementioned 2-valent linear aliphatic group has a structure having a side chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or the like.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the amount is not less than the lower limit, the development adhesion tends to be good, and when the amount is not more than the upper limit, the curability tends to be good. Specific examples of the 2-valent cyclic aliphatic group include: a group obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborneol ring, or an adamantane ring. Among these groups, from the viewpoint of reliability, a group obtained by removing 2 hydrogen atoms from the adamantane ring is preferable.
As the substituent optionally having the 2-valent aliphatic group, there can be mentioned: a hydroxyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
Examples of the 2-valent aromatic ring group include a 2-valent aromatic ring group and a 2-valent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the 2-valent aromatic hydrocarbon ring group, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, perylene,
The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the 2-valent aromatic heterocyclic group include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole rings having 2 free valences,
Among the 2-valent aromatic ring groups, a benzene ring having 2 free valences, a naphthalene ring having 2 free valences, or a fluorene ring having 2 free valences is preferable from the viewpoint of patterning, and a fluorene ring having 2 free valences is more preferable.
Examples of the substituent optionally contained in the aromatic ring having a valence of 2 include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, the non-substituted is preferable from the viewpoint of developing solubility and resistance to moisture absorption.
Examples of the group in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked include groups in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked.
The number of the 2-valent aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
The number of the 2-valent aromatic ring groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Specific examples of the group in which 1 or more aliphatic groups having a valence of 2 are linked to 1 or more aromatic groups having a valence of 2 include groups represented by the above formulas (i-A) to (i-E). Among these groups, the group represented by the above formula (i-a) is preferable from the viewpoint of reliability.
The bonding form of the cyclic hydrocarbon group of the side chain to these 2-valent hydrocarbon groups is not particularly limited, and examples thereof include an aliphatic group, a form in which 1 hydrogen atom of the aromatic ring group is substituted with a side chain, and a form in which 1 carbon atom containing the aliphatic group constitutes the cyclic hydrocarbon group of the side chain.
In addition, the partial structure represented by the above formula (ii) is preferably a partial structure represented by the following formula (ii-1) from the viewpoint of compatibility.
[ chemical formula 28]
In the formula (ii-1), R cR has the same meaning as the above formula (ii) αRepresents an optionally substituted 1-valent cyclic hydrocarbon group, n is an integer of 1 or more, and represents a bonding position. The benzene ring in the formula (ii-1) may be further substituted with an optional substituent.
(R α)
In the above formula (ii-1), R αRepresents a 1-valent cyclic hydrocarbon group optionally having a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less carbon atoms. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. Among these, an adamantane ring is preferable from the viewpoint of compatibility.
On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, further preferably 15 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, and the like. Among these, the fluorene ring is preferable from the viewpoint of reliability.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: a hydroxyl group; an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, etc.; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Of these, R is preferable from the viewpoint of compatibility αIs a 1-valent aliphatic ring group, and is more preferably an adamantyl group.
As described above, the benzene ring in the formula (ii-1) may be further substituted with an arbitrary substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of the substituents is not particularly limited, and may be 1, or 2 or more.
Among these, from the viewpoint of patterning characteristics, non-substitution is preferable.
Specific examples of the partial structure represented by the above formula (ii-1) are listed below.
[ chemical formula 29]
[ chemical formula 30]
[ chemical formula 31]
[ chemical formula 32]
[ chemical formula 33]
In addition, the partial structure represented by the above general formula (ii) is preferably a partial structure represented by the following general formula (ii-2) from the viewpoint of reliability.
[ chemical formula 34]
In the formula (ii-2), R cR has the same meaning as the above formula (ii) βRepresents a 2-valent cyclic hydrocarbon group optionally having a substituent, and represents a bonding position. The benzene ring in the formula (ii-2) may be further substituted with an optional substituent.
(R β)
In the above formula (ii-2), R βRepresents a 2-valent cyclic hydrocarbon group optionally having a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
The number of rings of the aliphatic ring group is not particularly limited, and is 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less carbon atoms. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. Among these, an adamantane ring is preferable from the viewpoint of compatibility.
On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, particularly preferably 15 or less. When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be good.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, and the like. Among these, the fluorene ring is preferable from the viewpoint of reliability.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: a hydroxyl group; an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, etc.; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
Among these, R is, from the viewpoint of compatibility βPreferably a 2-valent aliphatic ring group, more preferably a 2-valent adamantyl ring group.
On the other hand, from the viewpoint of reliability, R βPreferably a 2-valent aromatic ring group, more preferably a 2-valent fluorene ring group.
As described above, the benzene ring in the formula (ii-2) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of the substituents is also not particularly limited, and may be 1 or 2 or more. Further, 2 benzene rings in the formula (ii-2) may be linked via the above-mentioned substituent.
Among these, from the viewpoint of patterning characteristics, non-substitution is preferable.
Specific examples of the partial structure represented by the above formula (ii-2) are shown below.
[ chemical formula 35]
[ chemical formula 36]
[ chemical formula 37]
[ chemical formula 38]
On the other hand, the partial structure represented by the above general formula (ii) is preferably a partial structure represented by the following general formula (ii-3) from the viewpoint of compatibility.
[ chemical formula 39]
In the formula (ii-3), R cAnd R dR has the same meaning as the above formula (ii) ZRepresents a hydrogen atom or a polybasic acid residue.
The polybasic acid residue refers to a 1-valent group obtained by removing 1 OH group from a polybasic acid or an anhydride thereof. It is noted that 1 OH group may be further removed from the molecule and R in the other molecule represented by the formula (ii-3) ZCommon, i.e. can be through R ZA plurality of the formulae (ii-3) are linked.
The polybasic acid may be one or 2 or more selected from the group consisting of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethenyltetrahydrophthalic acid, hexachloronorbornene diacid, methyltetrahydrophthalic acid, and biphenyl tetracarboxylic acid.
Among these, from the viewpoint of patterning characteristics, the polybasic acid is preferably maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, or biphenyltetracarboxylic acid, and more preferably tetrahydrophthalic acid or biphenyltetracarboxylic acid.
The partial structure represented by the above formula (ii-3) contained in 1 molecule of the epoxy (meth) acrylate resin (b1-C) may be one type, or 2 or more types, and for example, R may be present in combination ZIs a hydrogen atom and R ZIs a polybasic acid residue.
The number of the partial structures represented by the above formula (II) contained in 1 molecule of the epoxy (meth) acrylate resin (b1-C) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. When the lower limit value is not less than the above-mentioned lower limit value, curability tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, developing solubility tends to be good.
The epoxy (meth) acrylate resin (b1) may be used alone or in combination of 2 or more kinds.
In addition, a part of the epoxy (meth) acrylate resin (b1) may be replaced with another binder resin. That is, the epoxy (meth) acrylate-based resin (b1) and other binder resins may be used in combination. In this case, the proportion of the epoxy (meth) acrylate resin (b1) in the alkali-soluble resin (b) is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, and most preferably 50% by mass or more. Further, it is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, and particularly preferably 60% by mass or less. The combination of the upper limit and the lower limit is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, particularly preferably 40 to 60% by mass, and most preferably 50 to 60% by mass.
The other binder resin that can be used in combination with the epoxy (meth) acrylate-based resin (b1) is not limited as long as it is selected from resins generally used for photosensitive coloring compositions. Examples thereof include binder resins described in, for example, Japanese patent application laid-open Nos. 2007-271727, 2007-316620, and 2007-334290. From the viewpoint of reliability and surface smoothness, a (meth) acrylic copolymer resin described in international publication No. 2017/110893 is preferable. The other binder resins may be used alone or in combination of 2 or more.
In addition, as the alkali-soluble resin (b), an acrylic resin (b2) is preferably used from the viewpoint of compatibility with a colorant, a dispersant, and the like.
Examples of the acrylic resin include: a copolymer of an ethylenically unsaturated monomer having 1 carboxyl group (hereinafter, referred to as "unsaturated monomer (b 2-1)") and another ethylenically unsaturated monomer copolymerizable therewith (hereinafter, referred to as "unsaturated monomer (b 2-2)").
Examples of the unsaturated monomer (b2-1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α -chloroacrylic acid and cinnamic acid, unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, citraconic anhydride and mesaconic acid or anhydrides thereof, mono [ (meth) acryloyloxyalkyl ] esters of 2-or more-membered polycarboxylic acids such as succinic acid mono [ 2- (meth) acryloyloxyethyl ] ester and phthalic acid mono [ 2- (meth) acryloyloxyethyl ] ester, mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends such as ω -carboxypolycaprolactone mono (meth) acrylate, and p-vinylbenzoic acid.
These unsaturated monomers (b2-1) may be used singly or in admixture of 2 or more.
Examples of the unsaturated monomer (b2-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide, aromatic vinyl compounds such as styrene, α -methylstyrene, p-hydroxystyrene, p-hydroxy- α -methylstyrene, p-vinylbenzyl glycidyl ether and acenaphthylene;
methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2-10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2-10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2-10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 2,6]Ethylene oxide-modified decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, and p-cumylphenol (meth)(meth) acrylates such as allyl) acrylate, glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3- [ (meth) acryloyloxymethyl ] oxetane and 3- [ (meth) acryloyloxymethyl ] -3-ethyloxetane;
cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 2,6]Vinyl ethers such as decan-8-yl vinyl ether, pentacyclopentadecyl vinyl ether and 3- (vinyloxymethyl) -3-ethyloxetane; and macromonomers having a mono (meth) acryloyl group at the terminal of the polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (b2-2) may be used singly or in admixture of 2 or more.
In the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2), the copolymerization ratio of the unsaturated monomer (b2-1) in the copolymer is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. When the unsaturated monomer (b2-1) is copolymerized in such a range, a photosensitive coloring composition having excellent alkali developability and storage stability tends to be obtained.
Specific examples of the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) include copolymers disclosed in, for example, Japanese patent application laid-open Nos. 7-140654, 8-259876, 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118, 2004-101728, 2018-9132 and the like.
The copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) can be produced by a known method, and the structure, Mw and Mw/Mn can be controlled by the methods disclosed in, for example, Japanese patent application laid-open Nos. 2003-222717, 2006-259680 and 2007/029871.
< (c) photopolymerization initiator
(c) The photopolymerization initiator is a component that directly absorbs light to cause a decomposition reaction or a hydrogen abstraction reaction, and has a function of generating a polymerization active radical. If necessary, an additive such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added.
Examples of the photopolymerization initiator include metallocene compounds containing a titanocene compound as described in, for example, Japanese patent application laid-open Nos. 59-152396 and 61-151197; hexaarylbiimidazole derivatives as described in Japanese patent laid-open No. 2000-56118; halomethylation described in Japanese patent application laid-open No. 10-39503
Specifically, for example, as the titanocene compound, there can be mentioned: dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyltitanium, dicyclopentadienyl bis (2,3,4,5, 6-pentafluorophenyl-1-yl) titanium, dicyclopentadienyl bis (2,3,5, 6-tetrafluorophenyl) titanium, dicyclopentadienyl bis (2,4, 6-trifluorophenyl) titanium, dicyclopentadienyl bis (2, 6-difluorophenyl) titanium, dicyclopentadienyl bis (2, 4-difluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2,3,4,5, 6-pentafluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2, 6-difluorophenyl) titanium, dicyclopentadienyl [2, 6-difluoro-3- (1-propyl) phenyl ] titanium, and the like.
Further, examples of the diimidazole derivatives include: 2- (2 '-chlorophenyl) -4, 5-diphenylimidazole 2-mer, 2- (2' -chlorophenyl) -4, 5-bis (3 '-methoxyphenyl) imidazole 2-mer, 2- (2' -fluorophenyl) -4, 5-diphenylimidazole 2-mer, 2- (2 '-methoxyphenyl) -4, 5-diphenylimidazole 2-mer, (4' -methoxyphenyl) -4, 5-diphenylimidazole 2-mer, and the like.
In addition, as halomethylation Oxadiazole derivatives, there may be mentioned: 2-trichloromethyl-5- (2' -benzofuranyl) -1,3,4-
Further, examples of the halomethyl-s-triazine derivatives include: 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-ethoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4, 6-bis (trichloromethyl) s-triazine and the like.
Examples of α -aminoalkylphenone derivatives include 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisopentylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1, 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, and 4- (diethylamino) chalcone.
The oxime ester compounds are particularly useful as photopolymerization initiators because they are effective in terms of sensitivity and platemaking property, and because the use of an alkali-soluble resin containing a phenolic hydroxyl group is disadvantageous in terms of sensitivity, such oxime ester compounds having excellent sensitivity are particularly useful. Since the oxime ester compound has a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals in the structure, the sensitivity is high even in a small amount and the reaction to heat is stable, and a photosensitive coloring composition having high sensitivity can be obtained in a small amount.
Examples of the oxime ester compound include compounds represented by the following general formula (IV).
[ chemical formula 40]
In the above formula (IV), R 21aRepresents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent, R 21bRepresents an optional substituent comprising an aromatic ring, R 22aRepresents an alkanoyl group optionally having a substituent or an aroyl group optionally having a substituent, and n represents an integer of 0 or 1.
R 21aThe number of carbon atoms of the alkyl group in (b) is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solubility in a solvent and sensitivity. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group.
Examples of the substituent optionally contained in the alkyl group include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, a 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl group, an N-acetyl-N-acetoxyamino group, and the like, and from the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.
As R 21aAs the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. The number of carbon atoms of the aromatic ring group is not particularly limited, and is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. From the viewpoint of developability, the amount is preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less.
Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, and the like, and among these, from the viewpoint of developability, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
Examples of the substituent optionally contained in the aromatic ring group include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group in which these substituents are linked to each other.
Among these, R is R from the viewpoint of developability 21aPreferred is an aromatic ring group optionally having a substituent, and more preferred is an aromatic ring group having an alkoxy group bonded to a substituent.
In addition, as R 21bPreferred are optionally substituted carbazolyl groups, optionally substituted thioxanthone groups or optionally substituted diphenylsulfide groups. Among these, an optionally substituted carbazolyl group is preferable from the viewpoint of sensitivity.
In addition, R 22aThe number of carbon atoms of the alkanoyl group in (b) is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less, from the viewpoint of solubility in a solvent and sensitivity. Specific examples of the alkanoyl group include acetyl, propionyl, and butyryl.
Examples of the substituent optionally contained in the alkanoyl group include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group and the like, and the substituent is preferably unsubstituted from the viewpoint of ease of synthesis.
In addition, R 22aThe number of carbon atoms of the aroyl group in (2) is not particularly limited, but is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solubility in a solvent and sensitivity. Specific examples of the aroyl group include benzoyl group and naphthoyl group.
Examples of the substituent optionally contained in the aroyl group include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, and the like, and from the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.
Of these, R is from the viewpoint of sensitivity 22aPreferred is an alkanoyl group optionally having a substituent, more preferred is an unsubstituted alkanoyl group, and further preferred is an acetyl group.
Further, from the viewpoint of reducing contamination of the liquid crystal layer by the colorant, it is also preferable to use the initiator described in Japanese patent laid-open publication No. 2016-133574.
The photopolymerization initiator may be used alone or in combination of 2 or more.
In order to improve the sensitivity, a sensitizing dye or a polymerization accelerator corresponding to the wavelength of the image exposure light source may be blended as necessary in the photopolymerization initiator. Examples of the sensitizing dye include: japanese patent laid-open Nos. 4-221958 and 4-219756
Among these sensitizing dyes, preferred is an amino group-containing sensitizing dye, and more preferred is a compound having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4 '-dimethylaminobenzophenones, 4' -diethylaminobenzophenones, 2-aminobenzophenone and 4-aminobenzophenoneBenzophenone compounds such as ketone, 4 '-diaminobenzophenone, 3' -diaminobenzophenone, and 3, 4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzo
The sensitizing dye may be used alone or in combination of 2 or more.
Examples of the polymerization accelerator include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as N-butylamine and N-methyldiethanolamine, and mercapto compounds described later.
The polymerization accelerator may be used alone or in combination of 2 or more.
< (d) an ethylenically unsaturated compound
The photosensitive coloring composition of the present invention comprises (d) an ethylenically unsaturated compound. By including (d) an ethylenically unsaturated compound, the sensitivity is improved.
The ethylenically unsaturated compound used in the present invention is a compound having at least 1 ethylenically unsaturated group in the molecule. Specific examples thereof include (meth) acrylic acid, alkyl (meth) acrylates, acrylonitrile, styrene, and monoesters of carboxylic acids having 1 ethylenically unsaturated bond and polyhydric alcohols or monohydric alcohols.
In the present invention, it is particularly preferable to use a polyfunctional ethylenic monomer having 2 or more ethylenically unsaturated groups in 1 molecule. The number of ethylenically unsaturated groups of the polyfunctional ethylenic monomer is not particularly limited, and is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 8 or less, more preferably 7 or less. When the lower limit value is not less than the above-mentioned lower limit value, the sensitivity tends to be high, and when the upper limit value is not more than the above-mentioned upper limit value, the solubility in a solvent tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 2 to 8, more preferably 4 to 8, and further preferably 5 to 7.
As examples of polyfunctional olefinic monomers, mention may be made, for example, of: esters of aliphatic polyols with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; esters obtained by esterification of a polyol such as an aliphatic polyol or an aromatic polyol with an unsaturated carboxylic acid or a polycarboxylic acid, and the like.
Examples of the ester of the aliphatic polyhydric compound and the unsaturated carboxylic acid include acrylic acid esters of aliphatic polyhydric compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, methacrylic acid esters obtained by replacing acrylic acid esters of these exemplified compounds with methacrylic acid esters, itaconic acid esters similarly obtained by replacing acrylic acid esters, crotonic acid esters obtained by replacing crotonic acid esters, and maleic acid esters obtained by replacing maleic acid esters.
Examples of the ester of an aromatic polyol and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of an aromatic polyol such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate and 1,2, 3-benzenetriol triacrylate.
The ester obtained by esterification of a polyvalent carboxylic acid and an unsaturated carboxylic acid with a polyhydric compound is not necessarily a single substance, and representative specific examples thereof include condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; a condensate of methacrylic acid, terephthalic acid and pentaerythritol; condensates of acrylic acid, adipic acid, butanediol, and glycerol, and the like.
Further, as examples of the polyfunctional ethylenic monomer used in the present invention, urethane (meth) acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or a polyol and a hydroxyl group-containing (meth) acrylate; epoxy acrylates such as addition reaction products of a polyhydric epoxy compound with hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate and the like are useful.
Examples of the urethane (meth) acrylates include: DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kagaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Ningmura chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyowa Kagaku Co., Ltd.), UV-1700B, UV-7600B, UV-7656 7605B, UV-7630B, UV7640 357640 7640B (manufactured by Nippon Kagaku Co., Ltd.), and the like.
Among these, from the viewpoint of curability, the ethylenically unsaturated compound (d) is preferably an alkyl (meth) acrylate, and more preferably dipentaerythritol hexaacrylate.
These may be used alone or in combination of 2 or more.
(e) solvent
The photosensitive coloring composition of the present invention may contain (e) a solvent. By including (e) a solvent, the pigment can be dispersed in the solvent, and there is a tendency that coating becomes easy.
The photosensitive coloring composition of the present invention is generally used in a state in which (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound, and other various components used as needed are dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferred from the viewpoint of dispersibility and coatability.
Among the organic solvents, from the viewpoint of coatability, it is preferable to select a solvent having a boiling point in the range of 100 to 300 ℃, and it is more preferable to select a solvent having a boiling point in the range of 120 to 280 ℃. The boiling point as used herein means a boiling point at a pressure of 1013.25hPa, and the boiling points are the same as below.
Examples of such an organic solvent include the following solvents.
Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;
glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;
glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;
glycol diacetate esters such as ethylene glycol diacetate, 1, 3-butanediol diacetate, and 1, 6-hexanediol diacetate;
alkyl acetates such as cyclohexyl acetate;
ethers such as amyl ether, ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;
ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone;
monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;
alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;
aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;
linear or cyclic esters such as amyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl decanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ -butyrolactone;
alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
halogenated hydrocarbons such as chlorobutane and chloropentane;
ether ketones such as methoxymethylpentanone;
nitriles such as acetonitrile and benzonitrile.
Examples of the commercially available organic solvent corresponding to the above-mentioned solvent include: mineral spirits (Mineral spirits), Varsol #2, Apco #18solvent, Apco trinner, sonal solvent nos. 1 and 2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("cellosolve" is a registered trademark, and the same applies hereinafter), ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether (diglyme) (all of which are trade names of the above), and the like.
These organic solvents may be used alone, or 2 or more kinds may be used in combination.
When the colored spacer is formed by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 200 ℃ as the organic solvent. More preferably an organic solvent having a boiling point of 120 to 170 ℃.
Among the above organic solvents, glycol alkyl ether acetates are preferable in terms of good balance of coatability, surface tension, and the like, and high solubility of the constituent components in the composition.
In addition, the glycol alkyl ether acetates may be used alone or in combination with other organic solvents. The organic solvent used in combination is particularly preferably a glycol monoalkyl ether. Among these, propylene glycol monomethyl ether is preferred in particular from the viewpoint of solubility of the constituent components in the composition. The glycol monoalkylethers have a high polarity, and if the amount added is too large, the pigment tends to aggregate easily, and the storage stability of the photosensitive coloring composition obtained thereafter tends to be lowered, for example, the viscosity of the composition increases, and therefore the proportion of the glycol monoalkylethers in the solvent is preferably 5 to 30% by mass, more preferably 5 to 20% by mass.
In addition, it is also preferably used in combination with an organic solvent having a boiling point of 150 ℃ or higher (hereinafter, sometimes referred to as "high-boiling solvent"). When the pigment is used in combination with such a high boiling point solvent, the photosensitive coloring composition is difficult to dry, but the pigment is prevented from being broken in a uniform dispersion state in the composition in the case of rapid drying. That is, for example, the effect of preventing the occurrence of foreign matter defects at the tip of the slit nozzle due to precipitation and solidification of a colorant or the like is obtained. Among the various solvents, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol mono-ethyl ether acetate are particularly preferable from the viewpoint of high effects.
When a high-boiling solvent is used in combination, the content of the high-boiling solvent in the organic solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass. When the lower limit value is not less than the above-described lower limit value, for example, the generation of foreign matter defects at the tip of the slit nozzle due to precipitation and solidification of a colorant or the like tends to be suppressed, and when the upper limit value is not more than the above-described upper limit value, the drying rate of the composition is suppressed from being lowered, and thus problems such as a tact failure in the reduced pressure drying process and pin marks in the pre-bake (pre-cake) tend to be suppressed.
The high boiling point solvent having a boiling point of 150 ℃ or higher may be a glycol alkyl ether acetate or a glycol alkyl ether, and in this case, the high boiling point solvent having a boiling point of 150 ℃ or higher may not be additionally contained.
Preferred high boiling point solvents include diethylene glycol mono-n-butyl ether acetate, diethylene glycol mono-ethyl ether acetate, dipropylene glycol methyl ether acetate, 1, 3-butanediol diacetate, 1, 6-hexanediol diacetate, and triacetin among the above solvents.
(f) dispersant
The photosensitive coloring composition of the present invention may contain (f) a dispersant for the purpose of finely dispersing the colorant (a) and stabilizing the dispersed state.
The dispersant (f) is preferably a polymer dispersant having a functional group, and further preferably a carboxyl group in view of dispersion stability; a phosphate group; a sulfonic acid group; or a base thereof; primary, secondary or tertiary amino groups; quaternary ammonium salt groups; a polymer dispersant derived from a functional group such as a nitrogen-containing heterocyclic group such as pyridine, pyrimidine or pyrazine. Among these, in particular, the pigment having a primary amino group, a secondary amino group or a tertiary amino group is particularly preferable from the viewpoint that the pigment can be dispersed with a small amount of a dispersant when dispersed; quaternary ammonium salt groups; a polymer dispersant derived from a basic functional group such as a nitrogen-containing heterocyclic group such as pyridine, pyrimidine or pyrazine.
Examples of the polymeric dispersant include: urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants comprising a macromonomer and an amino group-containing monomer, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
Specific examples of such a dispersant include EFKA (registered trademark, manufactured by BASF corporation), DISPERBYK (registered trademark, manufactured by BYK-Chemie corporation), Disparlon (registered trademark, manufactured by Nako chemical industries, Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol corporation), KP (manufactured by shin-Etsu chemical industries, Ltd.), Polyflow (manufactured by Kyoho chemical Co., Ltd.), Ajisper (registered trademark, manufactured by K.K.).
These polymeric dispersants may be used alone or in combination of 2 or more.
The weight average molecular weight (Mw) of the polymeric dispersant is usually 700 or more, preferably 1000 or more, and usually 100000 or less, preferably 50000 or less.
Among these, from the viewpoint of pigment dispersibility, the dispersant (f) preferably contains a urethane-based polymer dispersant having a functional group and/or an acrylic-based polymer dispersant, and particularly preferably contains an acrylic-based polymer dispersant.
In addition, from the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and a polyester bond and/or a polyether bond is preferable.
Examples of the urethane and acrylic polymer dispersants include DISPERBYK160 to 166, 182 series (both of urethane), DISPERBYK2000, 2001, BYK-LPN21116 and the like (both of acrylic) (all of which are manufactured by BYK-Chemie).
Specifically, the preferable chemical structure of the urethane polymer dispersant is exemplified by a dispersion resin having a weight average molecular weight of 1000 to 200000 obtained by reacting a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10000 and having 1 or 2 hydroxyl groups in the molecule, and a compound having an active hydrogen and a tertiary amino group in the molecule. The dispersion resin may be treated with a quaternizing agent such as benzyl chloride to convert all or a part of the tertiary amino groups into quaternary ammonium salt groups.
Examples of the polyisocyanate compound include aromatic diisocyanates such as p-phenylene diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, 4,4 ' -diphenylmethane diisocyanate, naphthalene-1, 5-diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4 ' -methylenebis (cyclohexyl isocyanate), omega ' -diisocyanate dimethylcyclohexane and other alicyclic diisocyanates, xylylene diisocyanate, α ', α ' -tetramethylxylylene diisocyanate and other aliphatic diisocyanates having an aromatic ring, lysine ester triisocyanate, undecane-1, 6, 11-triisocyanate, 1, 8-diisocyanate-4-isocyanatomethyloctane, hexamethylene-1, 3, 6-triisocyanate, bicycloheptane triisocyanate, triphenylmethane triisocyanate, thiophosphoric acid triisocyanate and their trimers, polyhydric alcohols and their adducts, and the like, and the use of one or more kinds of organic trimers, and the most preferably of these trimers is an organic trimer.
Examples of the method for producing an isocyanate trimer include the following methods: the polyisocyanate is partially trimerized with an isocyanate group using an appropriate trimerization catalyst, for example, tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc., and the trimerization is terminated by adding a catalyst poison, and then unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired polyisocyanate containing a trimerized isocyanate group.
Examples of the compound having a number average molecular weight of 300 to 10000 and having 1 or 2 hydroxyl groups in the molecule include polyether diol, polyester diol, polycarbonate diol, polyolefin diol, and the like, and those obtained by oxidizing one terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms, and mixtures of 2 or more of these compounds.
The polyether diol includes polyether diol, polyether ester diol, and a mixture of 2 or more of these diols. Examples of the polyether glycol include those obtained by homopolymerizing or copolymerizing an alkylene oxide, for example, polyethylene glycol, polypropylene glycol, polyethylene glycol propylene glycol, polyoxybutylene glycol, polyoxyhexylene glycol, polyoxyoctylene glycol, and a mixture of 2 or more thereof.
Examples of the polyether ester diol include those obtained by reacting a diol having an ether group or a mixture thereof with another diol with a dicarboxylic acid or an acid anhydride thereof, or by reacting an alkylene oxide with a polyester diol, such as poly (polyoxybutylene) adipate. The polyether glycol is most preferably polyethylene glycol, polypropylene glycol, polyoxybutylene glycol, or a compound obtained by oxidizing one terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms.
As the polyester diol, there may be mentioned: dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof with glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 2-methyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-methyl-2, 4-pentanediol, 2, 4-trimethyl-1, aliphatic diols such as 3-pentanediol, 2-ethyl-1, 3-hexanediol, 2, 5-dimethyl-2, 5-hexanediol, 1, 8-octanediol, 2-methyl-1, 8-octanediol, and 1, 9-nonanediol, alicyclic diols such as bis (hydroxymethyl) cyclohexane, aromatic diols such as benzenedimethanol and bis (hydroxyethoxy) benzene, and N-alkyldialkanolamines such as N-methyldiethanolamine) by polycondensation, for example, polyethylene adipate, polybutylene adipate, 1, 6-hexanediol adipate, and ethylene propylene glycol adipate, or polylactone diols or polylactone monools obtained by using the above diols or monools having 1 to 25 carbon atoms as an initiator, for example, polycaprolactone diol, polycaprolactone monool, and the like, Polymethyl valerolactone and a mixture of 2 or more thereof. The polyester diol is most preferably polycaprolactone diol or polycaprolactone obtained using an alcohol having 1 to 25 carbon atoms as an initiator.
The polycarbonate diol includes poly (1, 6-hexanediol) carbonate and poly (3-methyl-1, 5-pentanediol) carbonate, and the polyolefin diol includes polybutadiene diol, hydrogenated polyisoprene diol, and the like.
These may be used alone or in combination of 2 or more.
The number average molecular weight of the compound having 1 or 2 hydroxyl groups in the molecule is usually 300 to 10000, preferably 500 to 6000, and more preferably 1000 to 4000.
The compound having active hydrogen and tertiary amino group in the molecule used in the present invention will be described.
The active hydrogen, that is, the hydrogen atom directly bonded to the oxygen atom, nitrogen atom or sulfur atom, includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group or a mercapto group, and among them, a hydrogen atom of an amino group, particularly a primary amino group, is preferable.
The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
Examples of such compounds having active hydrogen and tertiary amino groups in the molecule include N, N-dimethyl-1, 3-propanediamine, N-diethyl-1, 3-propanediamine, N-dipropyl-1, 3-propanediamine, N-dibutyl-1, 3-propanediamine, N-dimethylethylenediamine, N-diethylethylenediamine, n, N-dipropylethylenediamine, N-dibutylethylenediamine, N-dimethyl-1, 4-butanediamine, N-diethyl-1, 4-butanediamine, N-dipropyl-1, 4-butanediamine, N-dibutyl-1, 4-butanediamine, and the like.
In addition, examples of the nitrogen-containing heterocycle in the case where the tertiary amino group has a nitrogen-containing heterocycle structure include: pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring
Specific examples of the compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, and 1- (2-aminoethyl) imidazole. Further, specific examples of such compounds having a triazole ring and an amino group include 3-amino-1, 2, 4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1, 2, 4-triazole, 4-amino-4H-1, 2, 4-triazole-3, 5-diol, 3-amino-5-phenyl-1H-1, 3, 4-triazole, 5-amino-1, 4-diphenyl-1, 2, 3-triazole, and 3-amino-1-benzyl-1H-2, 4-triazole. Among them, N-dimethyl-1, 3-propanediamine, N-diethyl-1, 3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1, 2, 4-triazole are preferable.
These may be used alone or in combination of 2 or more.
The preferable blending ratio of the raw materials for producing the urethane polymer dispersant is as follows: the amount of the compound having a number average molecular weight of 300 to 10000, which has 1 or 2 hydroxyl groups in the molecule, is 10 to 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and the amount of the compound having active hydrogen and tertiary amino groups in the molecule is 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass, based on 100 parts by mass of the polyisocyanate compound.
The urethane polymer dispersant is produced by a known method for producing a polyurethane resin. As the solvent in the production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; esters such as ethyl acetate, butyl acetate, cellosolve acetate, and the like; hydrocarbons such as benzene, toluene, xylene, and hexane; partial alcohols such as diacetone alcohol, isopropyl alcohol, sec-butyl alcohol and tert-butyl alcohol, and chlorinated substances such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; polar aprotic solvents such as dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide. These may be used alone or in combination of 2 or more.
In the above production, a urethane reaction catalyst is generally used. Examples of the catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and tin octylate, iron-based catalysts such as iron acetylacetonate and iron chloride, and tertiary amines such as triethylamine and triethylenediamine. These may be used alone or in combination of 2 or more.
The amount of the compound having active hydrogen and tertiary amino group introduced in the molecule is preferably an amount in which the amine value after the reaction is controlled to be in the range of 1 to 100mgKOH/g, more preferably an amount in the range of 5 to 95 mgKOH/g. The amine number is a value corresponding to an acid value in mg of KOH by neutralization titration of a basic amino group with an acid. When the amine value is less than the above range, the dispersibility tends to be lowered, and when the amine value exceeds the above range, the developability tends to be lowered.
In the case where an isocyanate group remains in the polymer dispersant in the above reaction, it is preferable that the product has high stability with time if the isocyanate group is further destroyed by an alcohol or an amino compound.
The weight average molecular weight (Mw) of the urethane polymer dispersant is usually 1000 to 200000, preferably 2000 to 100000, and more preferably 3000 to 50000. When the content is not less than the lower limit, dispersibility and dispersion stability tend to be improved, and when the content is not more than the upper limit, solubility tends to be improved and dispersibility tends to be improved.
On the other hand, as the acrylic polymer dispersant, a random copolymer, a graft copolymer, or a block copolymer of a monomer having a functional group (the functional group mentioned here is the functional group mentioned above as the functional group contained in the polymer dispersant) and containing an unsaturated group and a monomer having no functional group and containing an unsaturated group is preferably used. These copolymers can be produced by a known method.
Examples of the monomer having a functional group and containing an unsaturated group include unsaturated monomers having a carboxyl group such as (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, and acrylic acid dimer, and unsaturated monomers having a tertiary amino group or a quaternary ammonium group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and quaternary products thereof. These may be used alone or in combination of 2 or more.
Examples of the monomer having no functional group but containing an unsaturated group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, α -methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide and other N-substituted maleimides, acrylonitrile, vinyl acetate and a poly (meth) methyl acrylate macromonomer, a polystyrene macromonomer, a poly (meth) 2-hydroxyethyl acrylate macromonomer, a polyethylene glycol macromonomer, a polypropylene glycol macromonomer, a polycaprolactone macromonomer and the like.
The acrylic polymer dispersant is particularly preferably an a-B or B-a-B block copolymer composed of an a block having a functional group and a B block having no functional group, and in this case, the a block may contain a partial structure derived from the monomer not having a functional group but having an unsaturated group in addition to the partial structure derived from the monomer having a functional group and having an unsaturated group, and these structures may be contained in the a block in any form of random copolymerization or block copolymerization. The content of the partial structure containing no functional group in the a block is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.
The B block includes a partial structure derived from the above-mentioned monomer having no functional group but having an unsaturated group, and 1B block may contain a partial structure derived from 2 or more kinds of monomers, and these structures may be contained in the B block in any form of random copolymerization or block copolymerization.
The A-B or B-A-B block copolymer can be produced, for example, by the living polymerization method shown below. The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method, and a radical living polymerization method, wherein the polymerization living species of the anionic living polymerization method is an anion, and is represented by, for example, the following synthetic route.
[ chemical formula 41]
In the above synthetic scheme, Ar 1Is a 1-valent organic radical, Ar 2Is different from Ar 1M is a metal atom, and s and t are each an integer of 1 or more.
The polymerization active species of the radical active polymerization method is a radical, and is represented by, for example, the following synthetic route.
[ chemical formula 42]
In the above synthetic scheme, Ar 1Is a 1-valent organic radical, Ar 2Is different from Ar 1J and k are each an integer of 1 or more, R aIs a hydrogen atom or a 1-valent organic radical, R bAnd R aAnd, instead, is a hydrogen atom or a 1-valent organic group.
For the synthesis of the acrylic polymer dispersant, Japanese patent application laid-open No. 9-62002, P.Lutz, P.Masson et al, Polymer.Bull.12, 79(1984), B.C.Anderson, G.D.Andrews et al, Macromolecules,14,1601(1981), K.Hatada, K.Ute, et al, Polym.J.17,977(1985),18,1037(1986), Right hand Haoyi I, talking field I, polymer processing, 36,366(1987), Tomura Youngensis, Zeyan Guang male, polymer corpus, 46, 189(1989), M.Kuroki, T.Aida, J.Am.Chem.sic,109,4737(1987), Pingye Zhang Zhan, Pingyouping, organic synthetic chemistry, 43, 300. 1985, D.Y.Songhe.Her et al, 20,
1473(1987), and the like.
The acrylic polymer dispersant usable in the present invention may be an a-B block copolymer or a B-a-B block copolymer, and the ratio of a block/B block constituting the copolymer is preferably 1/99 to 80/20, particularly preferably 5/95 to 60/40 (mass ratio), and when the ratio is within this range, the balance between dispersibility and storage stability tends to be ensured.
In addition, in 1g of the A-B block copolymer and the B-A-B block copolymer which can be used in the present invention, the amount of the quaternary ammonium salt group is preferably 0.1 to 10mmol in general, and when the amount is in this range, good dispersibility tends to be ensured.
In such a block copolymer, an amino group generated in the production process may be contained, and the amine value thereof is about 1 to 100mgKOH/g, and from the viewpoint of dispersibility, it is preferably 10mgKOH/g or more, more preferably 30mgKOH/g or more, further preferably 50mgKOH/g or more, and preferably 90mgKOH/g or less, more preferably 80mgKOH/g or less, further preferably 75mgKOH/g or less. The combination of the upper limit and the lower limit is, for example, preferably 10 to 90mgKOH/g, more preferably 30 to 80mgKOH/g, and still more preferably 50 to 75 mgKOH/g.
Here, the amine value of the dispersant such as the block copolymer is represented by a KOH mass corresponding to the amount of base corresponding to 1g of the solid content excluding the solvent in the dispersant sample, and is measured by the following method.
0.5 to 1.5g of a dispersant sample was precisely weighed in a100 mL beaker, dissolved in 50mL of acetic acid, and subjected to a 0.1mol/L HClO solution using an automatic titrator equipped with a pH electrode 4The solution was subjected to neutralization titration with acetic acid solution, and the amine value was determined by the following equation, with the inflection point of the titration pH curve being set as the titration end point.
Amine value [ mgKOH/g ] (561 XV)/(W. times.S)
[ wherein, W: the weighed amounts of the dispersant samples [ g ], V: the titration amount [ mL ] at the end of titration, S: the solid content concentration [ mass% ] of the dispersant sample is shown. ]
The amine value of the block copolymer depends on the presence or absence of an acid group which is the base of the acid value and the type thereof, and is preferably a lower acid value, usually 10mgKOH/g or less, and the weight average molecular weight (Mw) is preferably in the range of 1000 to 100000. When the amount is within the above range, good dispersibility tends to be ensured.
When the acrylic polymer dispersant has a quaternary ammonium salt group as a functional group, the specific structure of the acrylic polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, the acrylic polymer dispersant preferably has a repeating unit represented by the following formula (i) (hereinafter, may be referred to as "repeating unit (i)").
[ chemical formula 43]
In the above formula (i), R 31～R 33Each independently being a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, an aralkyl group optionally having a substituent, R 31～R 332 or more of them may be bonded to each other to form a cyclic structure, R 34Is a hydrogen atom or a methyl group, X is a 2-valent linking group, Y -Are counter anions.
R of the above formula (i) 31～R 33The number of carbon atoms of the alkyl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 1 or more, and preferably 10 or less, and more preferably 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable. The polymer may be linear or branched. Further, the compound may have a cyclic structure such as cyclohexyl or cyclohexylmethyl.
R of the above formula (i) 31～R 33The number of carbon atoms of the aryl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 6 or more, and preferably 16 or less, and more preferably 12 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthryl group and the like, and among these, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group or a diethylphenyl group is preferable, and a phenyl group, a methylphenyl group or an ethylphenyl group is more preferable.
R of the above formula (i) 31～R 33Wherein the number of carbon atoms of the aralkyl group optionally having a substituent(s)The content is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group, and among these, a phenylmethyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group are preferable, and a phenylmethyl group or a phenylethyl group is more preferable.
Of these, R is preferable from the viewpoint of dispersibility 31～R 33Each independently is alkyl or aralkyl, specifically, R is preferred 31And R 33Each independently being methyl or ethyl, and R 32Is phenylmethyl or phenylethyl, more preferably R 31And R 33Is methyl and R 32Is a phenylmethyl group.
In addition, when the acrylic polymer dispersant has a tertiary amine as a functional group, it preferably has a repeating unit represented by the following formula (ii) (hereinafter, may be referred to as "repeating unit (ii)") from the viewpoint of dispersibility.
[ chemical formula 44]
In the above formula (ii), R 35And R 36Each independently being a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent or an aralkyl group optionally having a substituent, R 35And R 36May be bonded to each other to form a ring structure, R 37Is a hydrogen atom or a methyl group, and Z is a linking group having a valence of 2.
R in the above formula (ii) 35And R 36Wherein the alkyl group optionally having a substituent(s) may be preferably used as R in the above formula (i) 31～R 33But are exemplary groups.
Similarly, R is represented by the above formula (ii) 35And R 36Wherein the aryl group optionally having a substituent(s) may be preferably used as R in the above formula (i) 31～R 33But are exemplary groups. R in the above formula (ii) 35And R 36As the aralkyl group optionally having a substituent(s) in (1), R of the above-mentioned formula (i) can be preferably employed 31～R 33But are exemplary groups.
Of these, R 35And R 36Preferably each independently an optionally substituted alkyl group, more preferably a methyl or ethyl group.
R as the above formula (i) 31～R 33And R of the above formula (ii) 35And R 36Examples of the substituent optionally contained in the alkyl group, aralkyl group or aryl group in (1) include a halogen atom, an alkoxy group, a benzoyl group and a hydroxyl group.
In the above formulae (i) and (ii), examples of the 2-valent linking groups X and Z include: alkylene group having 1 to 10 carbon atoms, arylene group having 6 to 12 carbon atoms, -CONH-R 43-radical, -COOR 44A group [ wherein, R 43And R 44A single bond, an alkylene group having 1 to 10 carbon atoms or an ether group having 2 to 10 carbon atoms (an alkyloxyalkyl group)]Etc., preferably-COO-R 44-a radical.
In the formula (i), Y is a counter anion -Examples thereof include Cl -、Br -、I -、ClO 4 -、BF 4 -、CH 3COO -、PF 6 -And the like.
The content ratio of the repeating unit represented by the formula (i) is not particularly limited, but from the viewpoint of dispersibility, is preferably 60 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less, and particularly preferably 35 mol% or less, and is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and particularly preferably 30 mol% or more, relative to the total of the content ratio of the repeating unit represented by the formula (i) and the content ratio of the repeating unit represented by the formula (ii).
The content of the repeating unit represented by the formula (i) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, and preferably 50 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, and particularly preferably 15 mol% or less, from the viewpoint of dispersibility.
The content of the repeating unit represented by the above formula (ii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, particularly preferably 20 mol% or more, and preferably 60 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 25 mol% or less, from the viewpoint of dispersibility.
In addition, from the viewpoint of improving compatibility with a binder component such as a solvent and improving dispersion stability, the polymer dispersant preferably has a repeating unit represented by the following formula (iii) (hereinafter, may be referred to as "repeating unit (iii)").
[ chemical formula 45]
In the above formula (iii), R 40Is ethylene or propylene; r 41Is an alkyl group optionally having a substituent, R 42Is a hydrogen atom or a methyl group, and n is an integer of 1 to 20.
R of the above formula (iii) 41The number of carbon atoms of the alkyl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable. The polymer may be linear or branched. Further, the compound may have a cyclic structure such as cyclohexyl or cyclohexylmethyl.
In addition, n in the formula (iii) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, from the viewpoint of compatibility and dispersibility with respect to a binder component such as a solvent.
The content of the repeating unit represented by the above formula (iii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 4 mol% or more, and is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. When the amount is within the above range, compatibility with a binder component such as a solvent and dispersion stability tend to be achieved at the same time.
In addition, from the viewpoint of improving the compatibility of the dispersant with a binder component such as a solvent and improving dispersion stability, the polymeric dispersant preferably has a repeating unit represented by the following formula (iv) (hereinafter, may be referred to as "repeating unit (iv)").
[ chemical formula 46]
In the above formula (iv), R 38Is an alkyl group optionally having a substituent, an aryl group optionally having a substituent or an aralkyl group optionally having a substituent, R 39Is a hydrogen atom or a methyl group.
R of the above formula (iv) 38The number of carbon atoms of the alkyl group optionally having a substituent(s) in ((b) is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 4 or more, and preferably 10 or less, more preferably 8 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable. The polymer may be linear or branched. Further, the compound may have a cyclic structure such as cyclohexyl or cyclohexylmethyl.
R of the above formula (iv) 38The number of carbon atoms of the aryl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 6 or more, andand is preferably 16 or less, more preferably 12 or less, and further preferably 8 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthryl group and the like, and among these, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group or a diethylphenyl group is preferable, and a phenyl group, a methylphenyl group or an ethylphenyl group is more preferable.
R of the above formula (iv) 38The number of carbon atoms of the aralkyl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 7 or more, and is preferably 16 or less, more preferably 12 or less, and still more preferably 10 or less. Specific examples of the aralkyl group include a phenylmethylene, a phenylethylene, a phenylpropylene, a phenylbutylene, and a phenylisopropylene, and among these, a phenylmethylene, a phenylethylene, a phenylpropylene, and a phenylbutylene are preferable, and a phenylmethylene or a phenylethylene are more preferable.
Among these, R is from the viewpoint of solvent compatibility and dispersion stability 38Preferably an alkyl or aralkyl group, more preferably a methyl, ethyl or phenylmethylene group.
As R 38Examples of the substituent optionally contained in the alkyl group in (1) include a halogen atom and an alkoxy group. Examples of the substituent optionally contained in the aryl group or the aralkyl group include a linear alkyl group, a halogen atom, and an alkoxy group. In addition, R 38The chain alkyl group includes both straight-chain and branched-chain alkyl groups.
From the viewpoint of dispersibility, the content ratio of the repeating unit represented by the above formula (iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less.
The polymer dispersant may have a repeating unit other than the repeating unit (i), the repeating unit (ii), the repeating unit (iii) and the repeating unit (iv), and examples of such a repeating unit include repeating units derived from a styrene monomer such as styrene or α -methylstyrene, (meth) acryloyl chloride monomers such as meth) acryloyl chloride, (meth) acrylamide monomers such as meth) acrylamide and N-methylolacrylamide, (meth) acrylamide monomers such as vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether, and N-methacryloyl morpholine.
From the viewpoint of further improving the dispersibility, the polymeric dispersant is preferably a block copolymer having an a block having a repeating unit (i) and a repeating unit (ii) and a B block having no repeating unit (i) and no repeating unit (ii). The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. By introducing a quaternary ammonium salt group and a tertiary amino group into the a block, the dispersing ability of the dispersant tends to be remarkably improved. In addition, the B block preferably has a repeating unit (iii), and further preferably has a repeating unit (iv).
The a block may contain the repeating unit (i) and the repeating unit (ii) in any form of random copolymerization or block copolymerization. In addition, 1 a block may contain 2 or more kinds of the repeating unit (i) and the repeating unit (ii), and in this case, the a block may contain each repeating unit in any form of random copolymerization or block copolymerization.
The a block may contain a repeating unit other than the repeating unit (i) and the repeating unit (ii), and examples of such a repeating unit include a repeating unit derived from the above-mentioned (meth) acrylate monomer. The content of the repeating unit other than the repeating unit (i) and the repeating unit (ii) in the a block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and most preferably the a block does not contain the repeating unit.
The repeating units other than the repeating units (iii) and (iv) may be contained in the B block, and examples of such repeating units include repeating units derived from styrene monomers such as styrene and α -methylstyrene, (meth) acryloyl chloride monomers such as meth) acryloyl chloride, (meth) acrylamide monomers such as meth) acrylamide and N-methylolacrylamide, vinyl acetate, acrylonitrile, allyl glycidyl ether, glycidyl crotonate, and N-methacryloyl morpholine, and the content of the repeating units other than the repeating units (iii) and (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and most preferably the B block does not contain such repeating units.
In addition, from the viewpoint of improving dispersion stability, (f) a dispersant is preferably used in combination with a pigment derivative described later.
< other compounding ingredients of photosensitive coloring composition >
In addition to the above components, additives such as adhesion improving agents such as silane coupling agents, surfactants (coatability improving agents), pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, development improving agents, ultraviolet absorbers, and antioxidants can be suitably blended in the photosensitive coloring composition of the present invention.
(1) Adhesion improver
In order to improve adhesion to a substrate, an adhesion enhancer may be contained in the photosensitive coloring composition of the present invention. The adhesion improver is preferably a silane coupling agent, a compound containing a phosphoric group, or the like.
The silane coupling agent may be 1 kind of epoxy, meth (acrylic), or amino silane coupling agent, or 2 or more kinds of silane coupling agents may be used alone or in combination.
Preferred silane coupling agents include, for example: (meth) acryloyloxysilanes such as 3-methacryloyloxypropylmethyldimethoxysilane and 3-methacryloyloxypropyltrimethoxysilane, epoxysilanes such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane and isocyanatosilanes such as 3-isocyanatopropyltriethoxysilane, particularly preferred are the epoxysilanes.
The phosphoric acid group-containing compound is preferably a (meth) acryloyl group-containing phosphate ester, and more preferably a compound represented by the following general formula (g1), (g2) or (g 3).
[ chemical formula 47]
In the above general formulae (g1), (g2) and (g3), R 51Represents a hydrogen atom or a methyl group, l and l' are integers of 1 to 10, and m is 1,2 or 3.
These phosphoric acid group-containing compounds may be used alone or in combination of 2 or more.
(2) Surface active agent
In order to improve coatability, a surfactant may be contained in the photosensitive coloring composition of the present invention.
As the surfactant, various surfactants such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used. Among them, nonionic surfactants are preferably used from the viewpoint of low possibility of exerting adverse effects on various properties, and among them, fluorine-based and silicone-based surfactants are effective from the viewpoint of coatability.
Examples of such surfactants include: TSF4460 (manufactured by Momentive Performance materials), DFX-18 (manufactured by NEOS corporation), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie corporation), KP340 (manufactured by shin-Etsu Silicone Co., Ltd.), Megaface F-470, Megaface F-475, Megaface F-478, Megaface F-554, Megaface F-559 (manufactured by DIC corporation), SH7PA (manufactured by Dow Corning Toray Co., Ltd.), DS-401 (manufactured by Dajinko Co., Ltd.), L-77 (manufactured by Youica corporation, Japan), FC4430 (manufactured by 3M) and the like.
One kind of surfactant may be used, or 2 or more kinds may be used in combination in any combination and ratio.
(3) Pigment derivatives
The photosensitive coloring composition of the present invention may further contain a pigment derivative as a dispersing aid for improving dispersibility and storage stability.
Examples of the pigment derivative include azo compounds, phthalocyanine compounds, quinacridone compounds, benzimidazolone compounds, quinophthalone compounds, isoindolinone compounds, and bisquinophthalone compounds
Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, and the like, and these groups may be bonded to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group, and the like. In addition, a plurality of these substituents may be substituted on one pigment skeleton.
Specific examples of the pigment derivative include a phthalocyanine sulfonic acid derivative, a quinophthalone sulfonic acid derivative, an anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, and a diketopyrrolopyrrole sulfonic acid derivative Sulfonic acid derivatives of oxazines, and the like. These pigment derivatives may be used singly or in combination of 2 or more.
(4) Photoacid generators
The photo-acid generator is a compound capable of generating an acid by ultraviolet rays, and the photo-acid generator allows a crosslinking reaction to proceed in the presence of a crosslinking agent such as a melamine compound by the action of the acid generated during exposure. In such light productionAmong the acid agents, those having high solubility in a solvent, particularly in a solvent used for the photosensitive coloring composition, are preferable, and examples thereof include: diphenyl iodide
(5) Crosslinking agent
The photosensitive coloring composition of the present invention may further contain a crosslinking agent, and for example, a melamine or guanamine compound may be used. Examples of the crosslinking agent include melamine and guanamine compounds represented by the following general formula (6).
[ chemical formula 48]
In the formula (6), R 61represents-NR 66R 67A group or an aryl group having 6 to 12 carbon atoms, R 61is-NR 66R 67In the case of radicals, R 62、R 63、R 64、R 65、R 66And R 67represents-CH 2OR 68Radical, R 61When the aryl group has 6 to 12 carbon atoms, R 62、R 63、R 64And R 65represents-CH 2OR 68Radical, R 62、R 63、R 64、R 65、R 66And R 67The remaining radicals in (A) represent, independently of one another, hydrogen or-CH 2OR 68Radical, R 68Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
The aryl group having 6 to 12 carbon atoms is typically a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and these phenyl groups and naphthyl groups may have a substituent such as an alkyl group, an alkoxy group or a halogen atom bonded thereto. The number of carbon atoms of the alkyl group and the alkoxy group is about 1 to 6. In the above, R 68The alkyl group is a methyl group or an ethyl group, and a methyl group is particularly preferable.
The melamine-based compounds corresponding to the general formula (6), i.e., the compounds of the following general formula (6-1) include: hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethylmelamine, tetramethoxymethylmelamine, hexaethoxymethylmelamine, etc.
[ chemical formula 49]
In the formula (6-1), R 62、R 63、R 64、R 65、R 66And R 67In case one of (a) is an aryl group, R 62、R 63、R 64And R 65represents-CH 2OR 68Radical, R 62、R 63、R 64、R 65、R 66And R 67The remaining groups in (a) represent, independently of each other, a hydrogen atom or-CH 2OR 68Radical, R 68Represents a hydrogen atom or an alkyl group.
Guanamine compounds corresponding to the general formula (6), that is, R in the general formula (6) 61Compounds that are aryl groups include: tetramethylolbenzoguanamine, tetramethoxymethylbenzguanamine, trimethoxymethylbenzguanamine, tetraethoxymethylbenzguanamine, and the like.
In addition, crosslinkers having methylol or methylol alkyl ether groups may also be used. Examples thereof are listed below.
2, 6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2, 6-bis (hydroxymethyl) phenol, 5-ethyl-1, 3-bis (hydroxymethyl) perhydro-1, 3, 5-triazin-2-one (commonly known as N-ethyldimethylol triazinone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3, 5-bis (hydroxymethyl) perhydro-1, 3,5-
These crosslinking agents may be used alone or in combination of two or more. When the crosslinking agent is used, the amount thereof is preferably 0.1 to 15% by weight, particularly preferably 0.5 to 10% by weight, based on the total solid content of the photosensitive coloring composition.
(6) Mercapto compounds
In addition, a mercapto compound may be added as a polymerization accelerator in order to improve adhesion to the substrate.
Examples of the mercapto compound include 2-mercaptobenzothiazole and 2-mercaptobenzo
< amount of component to be added to photosensitive coloring composition >
In the photosensitive coloring composition of the present invention, the content of the colorant (a) is 23 mass% or less in the entire solid content of the photosensitive coloring composition. (a) Since the colorant is a component that does not elastically deform, it is considered that the mechanical properties of the colored spacer obtained by setting the content ratio thereof to the upper limit value or less are good.
(a) The content ratio of the colorant is not particularly limited as long as it is 23% by mass or less in the entire solid content of the photosensitive coloring composition, and is preferably 22% by mass or less, more preferably 20% by mass or less, further preferably 18% by mass or less, further preferably 16% by mass or less, particularly preferably 15% by mass or less, most preferably 14% by mass or less, and is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, further preferably 10% by mass or more, and particularly preferably 12% by mass or more. When the content ratio of the colorant (a) is equal to or less than the upper limit value, mechanical properties tend to be good, sufficient plate making properties tend to be easily obtained, and electrical reliability tends to be excellent. The combination of the upper limit and the lower limit is, for example, preferably 1 to 22 mass%, more preferably 5 to 20 mass%, still more preferably 8 to 18 mass%, still more preferably 10 to 16 mass%, particularly preferably 10 to 15 mass%, most preferably 12 to 14 mass%.
The content of the pigment in the photosensitive coloring composition of the present invention is not particularly limited, and is usually 23% by mass or less, preferably 22% by mass or less, more preferably 20% by mass or less, further preferably 18% by mass or less, further preferably 16% by mass or less, particularly preferably 15% by mass or less, and most preferably 14% by mass or less, and is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, further preferably 10% by mass or more, and particularly preferably 12% by mass or more, of the total solid content of the photosensitive coloring composition. When the content of the pigment is not more than the upper limit, mechanical properties tend to be good, sufficient plate-making properties tend to be easily obtained, and electrical reliability tends to be excellent. The combination of the upper limit and the lower limit is, for example, preferably 1 to 22 mass%, more preferably 5 to 20 mass%, still more preferably 8 to 18 mass%, still more preferably 10 to 16 mass%, particularly preferably 10 to 15 mass%, most preferably 12 to 14 mass%.
The content ratio of the orange pigment in the entire solid content of the photosensitive coloring composition according to
The photosensitive coloring composition according to
On the other hand, from the viewpoint of light-shielding properties, the blue pigment and/or the violet pigment may be contained, and in this case, the content ratio of the blue pigment and the violet pigment in the total solid content is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, particularly preferably 10% by mass or more, most preferably 15% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less. When the lower limit value is not less than the above-mentioned lower limit value, there is a tendency that sufficient light shielding properties can be obtained, and when the upper limit value is not more than the above-mentioned upper limit value, there is a tendency that a color tone close to black can be obtained. The combination of the upper limit and the lower limit is, for example, preferably 1 to 30% by mass, more preferably 5 to 30% by mass, still more preferably 8 to 25% by mass, still more preferably 10 to 20% by mass, and particularly preferably 15 to 20% by mass.
The photosensitive coloring composition of
On the other hand, from the viewpoint of suppressing the transmittance at a wavelength of 400 to 500nm, a yellow pigment may be contained, and in this case, the content ratio of the yellow pigment in the entire solid content is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, particularly preferably 10% by mass or more, most preferably 15% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less. When the lower limit value is set to the value not less than the lower limit value, the transmittance at a wavelength of 400 to 500nm tends to be suppressed, or a color tone close to black tends to be obtained, and when the upper limit value is set to the value not more than the upper limit value, the electrical reliability tends to be high, and the Optical Density (OD) tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 1 to 30% by mass, more preferably 3 to 30% by mass, still more preferably 5 to 30% by mass, yet more preferably 10 to 25% by mass, and particularly preferably 15 to 20% by mass.
The content of the alkali-soluble resin (b) is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 35% by mass or more, and is usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 45% by mass or less, in the entire solid content of the photosensitive coloring composition of the present invention. When the content ratio of the alkali-soluble resin (b) is not less than the lower limit, mechanical properties tend to be good and development tends to be good. Further, by setting the upper limit value or less, there is a tendency that the dissolution of the exposed portion in the developer can be suppressed while maintaining the appropriate sensitivity, and the decrease in the adhesion can be suppressed. The combination of the upper limit and the lower limit is, for example, preferably 5 to 85 mass%, more preferably 10 to 80 mass%, further preferably 20 to 70 mass%, further preferably 30 to 60 mass%, particularly preferably 35 to 50 mass%, most preferably 35 to 45 mass%.
The content of the photopolymerization initiator (c) is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more, and is usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 7% by mass or less, and particularly preferably 5% by mass or less, in the entire solid content of the photosensitive coloring composition of the present invention. When the content of the photopolymerization initiator (c) is not less than the lower limit, the sensitivity tends to be suppressed from decreasing, and when the content is not more than the upper limit, the solubility of the unexposed portion in the developer tends to be suppressed from decreasing, and the development failure tends to be suppressed. The combination of the upper limit and the lower limit is, for example, preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, still more preferably 1 to 8% by mass, still more preferably 2 to 7% by mass, and particularly preferably 2 to 5% by mass.
When the photopolymerization initiator (c) is used together with a polymerization accelerator, the content of the polymerization accelerator is preferably 0.05% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less, in the entire solid content of the photosensitive coloring composition of the present invention, and the polymerization accelerator is used usually in a proportion of 0.1 to 50 parts by mass, preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the photopolymerization initiator (c). When the content of the polymerization accelerator is not less than the lower limit, the sensitivity to the exposure light tends to be reduced, and when the content is not more than the upper limit, the solubility of the unexposed portion in the developer is reduced, and the development failure tends to be reduced.
When the sensitizing dye is used in addition to the photopolymerization initiator (c), the content of the sensitizing dye is usually 20 mass% or less, preferably 15 mass% or less, and more preferably 10 mass% or less of the total solid content of the photosensitive coloring composition from the viewpoint of sensitivity.
The content of the ethylenically unsaturated compound (d) is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 30% by mass or more, and is usually 70% by mass or less, preferably 60% by mass or less, and more preferably 50% by mass or less, in the entire solid content of the photosensitive coloring composition of the present invention. When the content ratio of the ethylenically unsaturated compound (d) is equal to or higher than the lower limit, there is a tendency that the dissolution of the exposed portion in the developer can be suppressed and the decrease in adhesion can be suppressed while maintaining appropriate sensitivity, and when the content ratio is equal to or lower than the upper limit, there is a tendency that the penetration of the developer into the exposed portion can be suppressed and a good image can be easily obtained. The combination of the upper limit and the lower limit is, for example, preferably 1 to 70% by mass, more preferably 5 to 60% by mass, still more preferably 10 to 60% by mass, yet more preferably 20 to 60% by mass, and particularly preferably 30 to 50% by mass.
On the other hand, the content of the (b) alkali-soluble resin is not particularly limited, but is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and further preferably 100 parts by mass or more, and is usually 700 parts by mass or less, preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and further preferably 300 parts by mass or less, with respect to 100 parts by mass of the (d) ethylenically unsaturated compound. When the lower limit value is not less than the above-described lower limit value, an appropriate development state without peeling or the like tends to be formed, and when the upper limit value is not more than the above-described upper limit value, an appropriate dissolution time with respect to the developer tends to be obtained. The combination of the upper limit and the lower limit is, for example, preferably 50 to 700 parts by mass, more preferably 80 to 500 parts by mass, still more preferably 80 to 400 parts by mass, and particularly preferably 100 to 300 parts by mass.
The photosensitive coloring composition of the present invention is prepared into a liquid by using the solvent (e) so that the content of the entire solid content is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more, and is usually 50% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less. The combination of the upper limit and the lower limit is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, and still more preferably 15 to 25% by mass.
When the photosensitive coloring composition of the present invention contains the dispersant (f), the content of the dispersant (f) in the entire solid content of the photosensitive coloring composition is usually 1% by mass or more, preferably 2% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less. When the content ratio of the dispersant (f) is equal to or higher than the lower limit, sufficient dispersibility tends to be easily obtained, and when the content ratio is equal to or lower than the upper limit, the ratio of other components tends to be relatively reduced, and a decrease in sensitivity, platemaking property, and the like tends to be suppressed. The combination of the upper limit and the lower limit is, for example, preferably 1 to 30% by mass, more preferably 1 to 20% by mass, still more preferably 1 to 15% by mass, yet more preferably 2 to 10% by mass, and particularly preferably 2 to 5% by mass.
The content of the dispersant (f) is usually 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and usually 50 parts by mass or less, particularly preferably 30 parts by mass or less, per 100 parts by mass of the colorant (a). When the content ratio of the dispersant (f) is equal to or higher than the lower limit, sufficient dispersibility tends to be easily obtained, and when the content ratio is equal to or lower than the upper limit, the ratio of other components tends to be relatively reduced, and a decrease in sensitivity, platemaking property, and the like tends to be suppressed. The combination of the upper limit and the lower limit is, for example, preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 15 to 30 parts by mass.
When the adhesion improver is used, the content of the adhesion improver is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4 to 2% by mass, in the entire solid content of the photosensitive coloring composition. When the content of the adhesion improver is not less than the lower limit, the effect of improving adhesion tends to be sufficiently obtained, and when the content is not more than the upper limit, the sensitivity reduction and the formation of defects due to residual residues after development tend to be suppressed.
When a surfactant is used, the content of the surfactant is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, and most preferably 0.03 to 0.3% by mass, of the total solid content in the photosensitive coloring composition. When the content ratio of the surfactant is equal to or higher than the lower limit value, smoothness and uniformity of the coating film tend to be easily exhibited, and when the content ratio is equal to or lower than the upper limit value, smoothness and uniformity of the coating film tend to be easily exhibited, and deterioration of other characteristics also tend to be suppressed.
< Properties of photosensitive coloring composition >
The photosensitive coloring composition of the invention can be suitably used for forming a colored spacer. From the viewpoint of use as a colored spacer, the cured film preferably has a high Optical Density (OD) corresponding to a film thickness of 1 μm. The optical density of the colored spacer alone obtained by curing the photosensitive colored composition of the present invention is preferably 0.01 or more, more preferably 0.03 or more, further preferably 0.05 or more, further preferably 0.08 or more, particularly preferably 0.10 or more, and most preferably 0.15 or more. Here, the Optical Density (OD) corresponding to a film thickness of 1 μm is a value measured by the method described in the examples described later.
When the color filter layer is laminated with a blue color filter layer, the Optical Density (OD) of 2 layers after the color spacer and the blue color filter layer are laminated is preferably 0.5 or more, and more preferably 1.0 or more. Here, the Optical Density (OD) of the 2 layers after lamination is a value measured by the method described in the examples described later.
In addition, in the photosensitive coloring composition of the invention, the ratio of the average absorbance at a wavelength of 400 to 500nm to the average absorbance at a wavelength of 500 to 700nm is preferably 1.8 or more, more preferably 2.0 or more, further preferably 3.0 or more, and is preferably 15 or less, more preferably 10 or less, further preferably 7 or less, and particularly preferably 4.5 or less. When the color filter layer is laminated with a blue color filter layer, the color tone tends to be close to black by setting the lower limit value or more. Further, by setting the upper limit value or less, the Optical Density (OD) tends to be increased.
Here, the ratio of the average absorbance at a wavelength of 400 to 500nm to the average absorbance at a wavelength of 500 to 700nm of the photosensitive coloring composition can be specified by forming a cured film having a film thickness of 2.5 μm using the photosensitive coloring composition and measuring the absorbance at a wavelength of 400 to 700nm at 1nm intervals using a spectrophotometer.
The detailed measurement conditions and the like are not particularly limited, and the measurement can be performed by the following method, for example.
First, a photosensitive coloring composition was applied on a glass substrate ("AN 100" manufactured by AGC corporation) using a spin coater, and then, the resultant was dried by heating at 90 ℃ for 90 seconds on a hot plate to form a coating film. The obtained coating film was irradiated with ultraviolet rays in the air. The intensity at 365nm of the used light is 32mW/cm 2The exposure amount of the ultraviolet ray of (4) is set to 70mJ/cm 2. Then, a developer solution containing 0.05 mass% of potassium hydroxide and 0.08 mass% of a nonionic surfactant (a-60, manufactured by kao corporation) was used, and after performing shower development at 25 ℃ under a water pressure of 0.15MPa, the development was terminated with pure water, and washing was performed by a water shower. The time of spraying and developing is adjusted between 10-120 seconds, and is set asThe time for which the exposed coating film was dissolved and removed was 1.5 times. The substrate with a coating film obtained in these procedures was heated in an oven at 230 ℃ for 20 minutes to fix the pattern, thereby obtaining a substrate with a cured film having a film thickness of 2.5 μm. Next, the absorbance of the substrate at a wavelength of 400 to 700nm was measured at 1nm intervals using a spectrophotometer UV-3150 manufactured by Shimadzu corporation as a control and a glass substrate not coated with the photosensitive coloring composition. Average absorbance is calculated by averaging the measured values of absorbance at intervals of 1nm at wavelengths of 400 to 500nm, average absorbance at wavelengths of 500 to 700nm is calculated in the same manner, and then the ratio of average absorbance at wavelengths of 400 to 500nm to average absorbance at wavelengths of 500 to 700nm is calculated.
The photosensitive coloring composition of the invention of embodiment 2 satisfies the chromaticity coordinates (x, y) of 0.40. ltoreq. x.ltoreq.0.55 and 0.35. ltoreq. y.ltoreq.0.50 in the xy chromaticity diagram. When the chromaticity coordinates (x, y) are within the above range, it is considered that the color tone is good when the blue layer is laminated, and light leakage at a wavelength of 400 to 500nm can be suppressed.
X is 0.40 or more, preferably 0.42 or more, more preferably 0.45 or more, and further preferably 0.46 or more. Further, x is 0.55 or less, preferably 0.53 or less, more preferably 0.52 or less, further preferably 0.51 or less, and particularly preferably 0.50 or less. When the lower limit value is not less than the above lower limit value, sufficient light shielding properties are secured, and transmittance at a wavelength of 400 to 500nm tends to be suppressed, and when the upper limit value is not more than the above upper limit value, mechanical properties tend to be improved. The combination of the upper limit and the lower limit is, for example, preferably 0.42 to 0.53, more preferably 0.45 to 0.52, still more preferably 0.46 to 0.51, and particularly preferably 0.46 to 0.50.
Y is 0.35 or more, preferably 0.37 or more, more preferably 0.40 or more, still more preferably 0.41 or more, and particularly preferably 0.42 or more. Y is 0.50 or less, preferably 0.48 or less, more preferably 0.47 or less, still more preferably 0.46 or less, and particularly preferably 0.45 or less. When the lower limit value is not less than the above lower limit value, sufficient light shielding properties are secured, and transmittance at a wavelength of 400 to 500nm tends to be suppressed, and when the upper limit value is not more than the above upper limit value, mechanical properties tend to be improved. The combination of the upper limit and the lower limit is, for example, preferably 0.37 to 0.48, more preferably 0.40 to 0.47, still more preferably 0.41 to 0.46, and particularly preferably 0.42 to 0.45.
Here, the chromaticity coordinates (x, y) in the xy chromaticity diagram can be specified by forming a cured film having a film thickness of 1.0 μm using the photosensitive coloring composition and measuring the spectroscopic spectrum.
The detailed measurement conditions and the like are not particularly limited, and the measurement can be performed by the following method, for example.
First, a photosensitive coloring composition was applied on a glass substrate ("AN 100" manufactured by AGC corporation) using a spin coater, and then, the resultant was dried by heating at 90 ℃ for 90 seconds on a hot plate to form a coating film. The obtained coating film was irradiated with ultraviolet rays in the air. The intensity at 365nm of the used light is 32mW/cm 2The exposure amount of the ultraviolet ray of (4) is set to 70mJ/cm 2. Then, a developer solution containing 0.05 mass% of potassium hydroxide and 0.08 mass% of a nonionic surfactant (a-60, manufactured by kao corporation) was used, and after performing shower development at 25 ℃ under a water pressure of 0.15MPa, the development was terminated with pure water, and washing was performed by a water shower. The shower developing time is adjusted to 10 to 120 seconds, and is 1.5 times the time for dissolving and removing the unexposed coating film. The substrate with a coating film obtained in these procedures was heated in an oven at 230 ℃ for 20 minutes to fix the pattern, thereby obtaining a substrate with a cured film having a film thickness of 1.0 μm. Then, the transmittance of the substrate was measured at 1nm intervals using a spectrophotometer UV-3150 manufactured by Shimadzu corporation and a glass substrate not coated with the photosensitive coloring composition as a control, and the transmittance of the substrate was measured at 380 to 780 nm. Then, chromaticity coordinates (x, y) of an xy chromaticity diagram in an XYZ color system are calculated from a graph (emission spectrum) of the transmittance at wavelengths of 380 to 780nm and the light source of FIG. 1.
< method for producing photosensitive coloring composition >
The photosensitive coloring composition of the present invention can be produced by a conventional method.
In general, the colorant (a) is preferably subjected to dispersion treatment in advance using a paint shaker, sand mill, ball mill, roll mill, stone mill, air mill, homogenizer, or the like. By the dispersion treatment, the colorant (a) is micronized, and thus the coating properties of the photosensitive coloring composition are improved.
The dispersion treatment is usually preferably performed in a system in which (a) a colorant, (e) a solvent, (f) a dispersant, and if necessary, (b) a part or all of an alkali-soluble resin are used in combination (hereinafter, the mixture to be subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as "ink" or "pigment dispersion liquid"). In particular, the use of a polymeric dispersant as the dispersant (f) is preferable because thickening of the obtained ink and photosensitive coloring composition over time can be suppressed (excellent dispersion stability).
Therefore, in the step of producing the photosensitive colored composition, it is preferable to produce a pigment dispersion liquid containing at least (a) a colorant, (e) a solvent, and (f) a dispersant. As the colorant (a), the solvent (e) and the dispersant (f) that can be used in the pigment dispersion liquid, those that can be used in the photosensitive coloring composition can be preferably used, respectively.
When the liquid containing all the components blended in the colored resin composition is subjected to the dispersion treatment, the highly reactive component may be modified due to heat generation during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system not containing (c) a photopolymerization initiator and (d) an ethylenically unsaturated compound.
When the colorant (a) is dispersed by a sand mill, glass beads or zirconia beads having a particle diameter of about 0.1 to 8mm are preferably used. The temperature of the dispersion treatment is usually in the range of 0 ℃ to 100 ℃, preferably in the range of room temperature to 80 ℃, and the suitable time of the dispersion treatment may be adjusted as appropriate, depending on the composition of the liquid, the size of the dispersion treatment apparatus, and the like. The approximate criteria for dispersion are: the gloss of the ink is controlled so that the 20-degree specular gloss (JIS Z8741) when the pigment dispersion or the photosensitive coloring composition is applied to a substrate is in the range of 50 to 300. When the lower limit value is not less than the above-described lower limit value, the following tendency is present: the residual coarse pigment ((a) colorant) particles due to insufficient dispersion treatment can be suppressed, and the developability, adhesion, resolution, and the like can be easily made sufficient. By setting the upper limit value to be equal to or lower than the above-described upper limit value, the following tendency is present: the generation of a large amount of ultrafine particles due to the pigment breakage can be suppressed, and the dispersion stability can be improved.
The pigment dispersed in the ink has a dispersion particle diameter of usually 0.03 to 0.3. mu.m. The particle size can be measured by a dynamic light scattering method or the like.
Next, the ink obtained by the dispersion treatment is mixed with the other components contained in the photosensitive coloring composition to prepare a uniform solution. In the production process of the photosensitive coloring composition, fine dust is often mixed into the liquid, and therefore the obtained photosensitive coloring composition is desired to be subjected to a filtration treatment by a filter or the like.
[ cured product ]
The cured product of the present invention can be obtained by curing the photosensitive colored composition of the present invention. A cured product obtained by curing the photosensitive colored composition can be preferably used as a colored spacer.
[ colored spacer ]
The colored spacer of the present invention composed of the cured product of the present invention will be described in terms of a method for producing the same.
(1) Support body
The material of the support for forming the colored spacer is not particularly limited as long as it has an appropriate strength. The transparent substrate is mainly used, and examples of the material thereof include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate and polysulfone, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins and poly (meth) acrylic resins, and various glasses. Among them, glass and heat-resistant resins are preferable from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. In addition to the transparent substrate, it may be formed on the TFT array.
In order to improve surface properties such as adhesiveness, the support may be subjected to corona discharge treatment, ozone treatment, film formation treatment of various resins such as a silane coupling agent and a urethane resin, or the like, as necessary.
The thickness of the transparent substrate is usually 0.05 to 10mm, preferably 0.1 to 7 mm. When a thin film forming treatment is performed on various resins, the thickness of the film is usually 0.01 to 10 μm, preferably 0.05 to 5 μm.
(2) Colored spacer
The photosensitive coloring composition of the present invention is used in the same applications as those of known photosensitive coloring compositions for color filters, and a method for forming the photosensitive coloring composition is described below with respect to the case of using the composition as a colored spacer.
Generally, a photosensitive coloring composition is supplied in a film or pattern form by a method such as coating on a support on which a coloring spacer is to be provided, and the solvent is dried. Next, a pattern is formed by a method such as photolithography in which exposure and development are performed. If necessary, additional exposure and thermosetting treatment are performed to form a colored spacer on the support.
(3) Formation of colored spacers
[1] Method for supplying substrate
The photosensitive coloring composition of the present invention is usually supplied onto a support in a state of being dissolved or dispersed in a solvent. The supply method may be performed by a conventionally known method, for example, spin coating, Wire bar (Wire bar) method, flow coating, die coating, roll coating, spray coating, or the like. In addition, the pattern may be formed by supplying by an ink jet method, a printing method, or the like. Among these, the use amount of the coating liquid can be greatly reduced by the die coating method, and the effect of fogging or the like attached when the spin coating method is used is completely eliminated, and generation of foreign matter or the like can be suppressed.
The amount of coating varies depending on the application, and for example, in the case of a colored spacer, the amount is usually in the range of 0.5 to 10 μm, preferably 1 to 9 μm, and particularly preferably 1 to 7 μm in terms of dry film thickness. In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire substrate. If the unevenness is large, a defect such as display unevenness occurs in the liquid crystal panel.
However, when the colored spacers having different heights are formed at one time by photolithography using the photosensitive colored composition of the present invention, the heights of the colored spacers to be finally formed are different.
As the support, a known substrate such as a glass substrate can be used. In addition, the substrate surface is preferably planar.
[2] Drying method
The drying after the supply of the photosensitive coloring composition solution onto the support is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Further, a reduced-pressure drying method of drying in a reduced-pressure chamber without increasing the temperature may be combined.
The drying temperature and drying time and drying conditions may be appropriately selected depending on the kind of the solvent component, the performance of the dryer to be used, and the like. The temperature is usually 40 to 130 ℃ for 15 seconds to 5 minutes, preferably 50 to 110 ℃ for 30 seconds to 3 minutes.
[3] Exposure method
The exposure is performed by a light source that superimposes a negative mask pattern on a coating film of the photosensitive coloring composition and irradiates ultraviolet rays or visible rays through the mask pattern. When exposure is performed using an exposure mask, a method of bringing the exposure mask close to a coating film of the photosensitive coloring composition; a method of disposing an exposure mask at a position distant from a coating film of the photosensitive coloring composition and projecting exposure light through the exposure mask. In addition, a scanning exposure method using laser light without using a mask pattern may be employed. In this case, exposure may be performed in a deoxygenated atmosphere or after an oxygen barrier layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer, if necessary, in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen.
In a preferred embodiment of the present invention, when the color spacers having different heights are simultaneously formed by photolithography, for example, an exposure mask having a light-shielding portion (light transmittance of 0%) and an opening (intermediate transmission opening) having an average light transmittance, which is the average light transmittance of a plurality of openings, smaller than that of an opening (full transmission opening) having the highest average light transmittance is used. In this method, a difference in residual film ratio is caused by a difference in average light transmittance between the intermediate transmission opening and the full transmission opening, that is, a difference in exposure amount.
For example, a method of forming a middle transmission opening portion by a matrix-like light-shielding pattern having fine polygonal light-shielding cells is known. Further, a method of controlling light transmittance by a film of a material such as chromium, molybdenum, tungsten, or silicon as an absorber is known.
The light source used for the exposure is not particularly limited. Examples of the light source include: lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; and laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium-cadmium laser, violet semiconductor laser, and near-infrared semiconductor laser. When light of a specific wavelength is used for irradiation, an optical filter may be used.
The optical filter may be of a type that can control the light transmittance of the exposure wavelength with a thin film, and examples of the material in this case include Cr compounds (e.g., Cr oxides, nitrides, oxynitrides, and fluorides), MoSi, Si, W, and Al.
The exposure dose is usually 1mJ/cm 2Above, preferably 5mJ/cm 2More preferably 10mJ/cm or more 2Above, and typically 300mJ/cm 2Below, preferably 200mJ/cm 2Below, more preferably 150mJ/cm 2The following.
In the case of the proximity exposure method, the distance between the exposure object and the mask pattern is usually 10 μm or more, preferably 50 μm or more, and more preferably 75 μm or more, and is usually 500 μm or less, preferably 400 μm or less, and more preferably 300 μm or less.
[4] Developing method
After the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of a basic compound or an organic solvent. In the aqueous solution, a surfactant, an organic solvent, a buffer, a complexing agent, a dye or a pigment may be further contained.
As the basic compound, there may be mentioned: inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, and organic basic compounds such as monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or trimethylamine, monoethylamine, diethylamine or triethylamine, monoisopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These basic compounds may be a mixture of 2 or more.
Examples of the surfactant include: nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinates; amphoteric surfactants such as alkylbetaines and amino acids.
Examples of the organic solvent include: isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, and the like. The organic solvent may be used alone or in combination with an aqueous solution.
The conditions of the development treatment are not particularly limited, and the development treatment can be carried out by any of the development methods such as a dip development method, a spray development method, a brush development method, and an ultrasonic development method at a development temperature of usually 10 to 50 ℃, preferably 15 to 45 ℃, particularly preferably 20 to 40 ℃.
[5] Additional exposure and thermal curing treatment
The substrate after development may be additionally exposed as necessary in the same manner as the above-described exposure method, or may be subjected to a heat curing treatment. The heat curing conditions at this time were as follows: the temperature is selected in the range of 100 to 280 ℃, preferably 150 to 250 ℃, and the time is selected in the range of 5 to 60 minutes.
The size, shape and the like of the colored spacer of the present invention can be adjusted according to the specification and the like of a color filter using the same, and the photosensitive colored composition of the present invention is useful particularly for simultaneously forming colored spacers having different heights between the spacer and the auxiliary spacer by photolithography, and in this case, the height of the spacer is usually about 2 to 7 μm, and the height of the auxiliary spacer is usually about 0.2 to 1.5 μm lower than the spacer.
[ color filters ]
The color filter of the present invention is provided with the colored spacer of the present invention as described above, and is manufactured by, for example, laminating a black matrix, red, green, and blue pixel colored layers, and a surface coating layer on a glass substrate as a transparent substrate to form the colored spacer, and then forming an alignment film. Alternatively, the pixel coloring layer and the coloring spacer may be formed on the liquid crystal driving side substrate, or may be formed on the transparent substrate and the liquid crystal driving side substrate, respectively.
Further, as described in Korean laid-open patent Nos. 10-2013-0015734, 10-2015-0059026, and 10-2017-0017447, colored spacers may be provided in the non-display region, and in this case, leakage of light in the non-display region can be reduced by laminating a blue layer and a red layer as color filters on the opposite side. Alternatively, only the blue layer, only the red layer, and only the green layer may be used. A liquid crystal display having an LED backlight tends to have a strong blue light component of the LED. Therefore, the blue light component is easily transmitted, and for example, in the case of only a single layer, particularly only a blue layer, light leakage at a wavelength of 400 to 500nm tends to occur easily. The light leakage can be controlled by the material characteristics of the laminated structure or the opposing colored spacer when the liquid crystal display is produced, and for example, it is preferable to use a colored spacer obtained by curing the photosensitive colored composition of the present invention.
[ image display apparatus ]
The image display device of the present invention includes the colored spacer of the present invention.
For example, the image display device of the present invention, such as a liquid crystal display device having the color spacer of the present invention, can be manufactured by laminating the color filter having the color spacer of the present invention described above to a liquid crystal driving side substrate to form a liquid crystal cell, and injecting liquid crystal into the formed liquid crystal cell.
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