阅读说明：本技术 感光性树脂组合物、固化膜、滤色器、固体摄像元件及图像显示装置 (Photosensitive resin composition, cured film, color filter, solid-state imaging element, and image display device ) 是由 奈良裕树 于 2020-05-20 设计创作，主要内容包括：本发明提供一种感光性树脂组合物,其含有：着色剂、树脂、聚合性化合物、光聚合引发剂、紫外线吸收剂及溶剂,所述感光性树脂组合物中,着色剂含有选自比色指数颜料蓝15:3及比色指数颜料蓝15:4中的至少1种酞菁颜料,并且在着色剂中含有50质量％以上的上述酞菁颜料,在感光性树脂组合物的总固体成分中含有0.1～10质量％的紫外线吸收剂。本发明还提供一种使用感光性树脂组合物而成的固化膜、滤色器、固体摄像元件及图像显示装置。(The invention provides a photosensitive resin composition, which contains: the photosensitive resin composition comprises a colorant, a resin, a polymerizable compound, a photopolymerization initiator, an ultraviolet absorber and a solvent, wherein the colorant contains at least 1 phthalocyanine pigment selected from color index pigment blue 15:3 and color index pigment blue 15:4, the colorant contains more than 50 mass% of the phthalocyanine pigment, and the ultraviolet absorber is contained in an amount of 0.1-10 mass% based on the total solid content of the photosensitive resin composition. The invention also provides a cured film, a color filter, a solid-state imaging element and an image display device which are formed by using the photosensitive resin composition.)

1. A photosensitive resin composition comprising a colorant, a resin, a polymerizable compound, a photopolymerization initiator, an ultraviolet absorber and a solvent,

the colorant contains at least 1 phthalocyanine pigment selected from color index pigment blue 15:3 and color index pigment blue 15:4, and the colorant contains 50% by mass or more of the phthalocyanine pigment,

the ultraviolet absorber is contained in an amount of 0.1 to 10 mass% based on the total solid content of the photosensitive resin composition.

2. The photosensitive resin composition according to claim 1, wherein the phthalocyanine pigment has an average secondary particle diameter of 50nm to 100 nm.

3. The photosensitive resin composition according to claim 1 or 2, wherein the colorant is contained in an amount of 10 mass% or more based on the total solid content of the photosensitive resin composition.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the resin contains a resin having an amine value of 25mgKOH/g to 60 mgKOH/g.

5. The photosensitive resin composition according to claim 4, wherein the resin having an amine value of 25mgKOH/g to 60mgKOH/g is a (meth) acrylic resin.

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the resin comprises an alkali-soluble resin.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the ultraviolet absorber is contained in an amount of 1 to 200 parts by mass per 100 parts by mass of the photopolymerization initiator.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the ultraviolet absorber is contained in an amount of 0.1 to 100 parts by mass based on 100 parts by mass of the polymerizable compound.

9. The photosensitive resin composition according to any one of claims 1 to 8, which is used for forming a pixel of a color filter.

10. The photosensitive resin composition according to claim 9, which is used for forming a cyan pixel.

11. The photosensitive resin composition according to any one of claims 1 to 10, which is used for a solid-state imaging element.

12. A cured film obtained from the photosensitive resin composition according to any one of claims 1 to 11.

13. A color filter having the cured film of claim 12.

14. A solid-state imaging element having the cured film according to claim 12.

15. The solid-state imaging element according to claim 14,

the cured film is a cyan pixel, and the solid-state imaging element further includes a yellow pixel and a magenta pixel.

16. An image display device having the cured film according to claim 12.

Technical Field

The present invention relates to a photosensitive resin composition containing at least 1 phthalocyanine pigment selected from color index pigment blue 15:3 and color index pigment blue 15: 4. The present invention also relates to a cured film, a color filter, a solid-state imaging device, and an image display device, each of which is formed using the photosensitive resin composition.

Background

In recent years, with the spread of digital cameras, mobile phones with cameras, and the like, the demand for solid-state imaging devices such as Charge Coupled Device (CCD) image sensors has increased dramatically. As a core device of a display or an optical element, a color filter is used.

As the color filter, a color filter of an additive color mixing method including red pixels, green pixels, and blue pixels, a color filter of a subtractive color mixing method including cyan pixels, magenta pixels, and yellow pixels, and the like are known. Pixels of each color of the color filter are manufactured using a photosensitive resin composition containing a colorant or the like.

Paragraphs 0123 to 0130 of patent document 1 describe a cyan photosensitive coloring composition comprising: the color-changing paint comprises a pigment dispersion with a color index pigment blue 15:3, an acrylic resin solution, a photo-polymerization monomer, a photo-polymerization initiator, a flatting agent solution and a solvent.

Patent document 2 describes a photosensitive colored resin composition for a color filter, which contains: the color index pigment comprises color index pigment green 7, a blue color material, a yellow color material, a dispersing agent, alkali-soluble resin, a multifunctional monomer, a photoinitiator and a solvent. Paragraph 0113 of patent document 2 describes that pigment blue 15:3, pigment blue 15:4, pigment blue 15:6, and the like are used as blue color materials.

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2017-142372

Patent document 2: japanese patent laid-open publication No. 2018-045189

Disclosure of Invention

Technical problem to be solved by the invention

In general, a color filter has pixels of a plurality of colors. The color filter having these pixels of a plurality of colors is manufactured by sequentially forming pixels of each color. For example, in the case of forming a color filter having pixels of a plurality of colors by photolithography using a photosensitive resin composition, the color filter is manufactured by performing the following operations for each color pixel: the photosensitive resin composition layer is formed on a support using a photosensitive resin composition, and then the photosensitive resin composition layer is exposed in a pattern, and then unexposed portions of the photosensitive resin composition layer are removed by development to form a pattern (pixel). Therefore, the photosensitive resin composition of another color formed in the next step may be applied to the pixel formed in the previous step (hereinafter, also referred to as the 1 st pixel). The photosensitive resin composition of the other color applied to the pixel (1 st pixel) formed in the previous step is removed by development treatment at the time of pattern formation, but if the 1 st pixel has insufficient curability or the like, the colorant or the like contained in the photosensitive resin composition of the other color applied to the 1 st pixel may move to the 1 st pixel side, causing color mixing. Therefore, it is desirable that the color mixture with pixels of other hues is small for pixels formed using the photosensitive resin composition. Further, pixels used for color filters are also required to have excellent spectral characteristics, excellent light resistance, and the like. Further, in recent years, higher-level juxtaposition is required for these characteristics.

However, as far as the cyan photosensitive resin composition for pixel formation has not been studied in depth, it has been difficult to form a cured film such as a pixel suitable for the spectral characteristics and light resistance of cyan and suppressing color mixing with pixels of other hues, which can be juxtaposed at a high level required in recent years, in a conventionally known cyan photosensitive resin composition for pixel formation. Further, according to the studies of the present inventors, it has been found that the compositions described in patent documents 1 and 2 have room for further improvement in these properties.

Accordingly, an object of the present invention is to provide a photosensitive resin composition, a cured film, a color filter, a solid-state imaging element, and an image display device, which are capable of forming a cured film having spectral characteristics suitable for developing cyan, excellent light resistance, and capable of suppressing color mixing with pixels of other hues.

Means for solving the technical problem

As a result of intensive studies, the present inventors have found that a cured film having spectral characteristics suitable for cyan can be improved by increasing the content of at least 1 phthalocyanine pigment selected from color index (c.i.) pigment blue 15:3 and c.i. pigment blue 15:4 in a colorant contained in a photosensitive resin composition. Further, the present inventors have further studied a cured film obtained by using the photosensitive resin composition, and as a result, they have found that there is still room for improvement in light resistance. The present inventors have further studied and found that a cured film having spectral characteristics suitable for cyan, excellent light resistance, and suppressed color mixing with pixels of other hues can be formed by using a composition containing 50 mass% or more of at least 1 phthalocyanine pigment selected from c.i. pigment blue 15:3 and c.i. pigment blue 15:4 as a colorant and containing 0.1 to 10 mass% of an ultraviolet absorber in the total solid content of the photosensitive resin composition, and have completed the present invention. The present invention provides the following.

< 1 > a photosensitive resin composition comprising: a colorant, a resin, a polymerizable compound, a photopolymerization initiator, an ultraviolet absorber and a solvent, wherein in the photosensitive resin composition,

the colorant contains at least 1 phthalocyanine pigment selected from color index pigment blue 15:3 and color index pigment blue 15:4, and contains more than 50% by mass of phthalocyanine pigment,

the photosensitive resin composition contains 0.1 to 10 mass% of an ultraviolet absorber in the total solid content.

< 2 > the photosensitive resin composition according to < 1 >, wherein the phthalocyanine pigment has an average secondary particle diameter of 50 to 100 nm.

< 3 > the photosensitive resin composition according to < 1 > or < 2 >, wherein the colorant is contained in an amount of 10 mass% or more based on the total solid content of the photosensitive resin composition.

< 4 > the photosensitive resin composition according to any one of < 1 > to < 3 >, wherein the resin contains a resin having an amine value of 25 to 60 mgKOH/g.

< 5 > the photosensitive resin composition according to < 4 >, wherein the resin having an amine value of 25 to 60mgKOH/g is a (meth) acrylic resin.

< 6 > the photosensitive resin composition according to any one of < 1 > to < 5 >, wherein the resin contains an alkali-soluble resin.

< 7 > the photosensitive resin composition according to any one of < 1 > to < 6 >, wherein the ultraviolet absorber is contained in an amount of 1 to 200 parts by mass based on 100 parts by mass of the photopolymerization initiator.

< 8 > the photosensitive resin composition according to any one of < 1 > to < 7 >, wherein the ultraviolet absorber is contained in an amount of 0.1 to 100 parts by mass based on 100 parts by mass of the polymerizable compound.

< 9 > the photosensitive resin composition according to any one of < 1 > to < 8 > Annona for forming pixels of color filters.

< 10 > the photosensitive resin composition according to < 9 > for forming a pixel of cyan.

< 11 > the photosensitive resin composition according to any one of < 1 > to < 10 > for use in a solid-state image pickup element.

< 12 > a cured film obtained from the photosensitive resin composition described in any of < 1 > to < 11 >.

< 13 > a color filter having < 12 > said cured film.

< 14 > a solid-state image pickup element having < 12 > the cured film.

< 15 > the solid-state imaging element according to < 14 >, wherein the cured film is a cyan pixel, and the solid-state imaging element further includes a yellow pixel and a magenta pixel.

< 16 > an image display device having < 12 > said cured film.

Effects of the invention

According to the present invention, it is possible to provide a photosensitive resin composition, a cured film, a color filter, a solid-state imaging element, and an image display device, which are capable of forming a cured film having spectral characteristics suitable for developing cyan, excellent light resistance, and capable of suppressing color mixing with pixels of other hues.

Detailed Description

The present invention will be described in detail below.

In the present specification, "to" means that the numerical values before and after "to" are included as the lower limit value and the upper limit value.

In the present specification, the label of a group (atomic group) is not described to include both a group (atomic group) having no substituent and a group (atomic group) having a substituent, both of which are substituted and unsubstituted. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "exposure" is not particularly limited, and in addition to exposure using light, drawing using a particle beam such as an electron beam or an ion beam is also included in exposure. Examples of the light used for exposure include actinic rays or radiation such as far ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, and electron beams, which are typically represented by the bright line spectrum of a mercury lamp or an excimer laser.

In the present specification, "(meth) acrylate" represents both or either of acrylate and methyl acrylate, "(meth) acrylic acid" represents both or either of acrylic acid and methacrylic acid, and "(meth) acryloyl group" represents both or either of acryloyl group and methacryloyl group.

In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In the present specification, the weight average molecular weight and the number average molecular weight are values in terms of polystyrene measured by a GPC (gel permeation chromatography) method.

In the present specification, the total solid content means the total mass of the components after removing the solvent from all the components of the composition.

In the present specification, a pigment means a compound which is not easily dissolved in a solvent.

In the present specification, the term "step" is not limited to a separate step, and is also included in the term if the action expected in the step is achieved even when the step cannot be clearly distinguished from other steps.

< photosensitive resin composition >

The photosensitive resin composition of the present invention contains:

a colorant, a resin, a polymerizable compound, a photopolymerization initiator, an ultraviolet absorber and a solvent, wherein the photosensitive resin composition is characterized in that,

the colorant contains at least 1 phthalocyanine pigment selected from color index pigment blue 15:3 and color index pigment blue 15:4, and the colorant contains 50% by mass or more of the phthalocyanine pigment,

the ultraviolet absorber is contained in an amount of 0.1 to 10 mass% based on the total solid content of the photosensitive resin composition.

According to the photosensitive resin composition of the present invention, a cured film having spectral characteristics suitable for developing cyan, excellent light resistance, and suppressed color mixing with pixels of other hues can be formed. In particular, a cured film having a high average transmittance for light having a wavelength of 400 to 530nm and a low average transmittance for light having a wavelength of 610 to 700nm can be formed. A cured film having spectral characteristics suitable for cyan can be formed by using a colorant containing 50 mass% or more of at least 1 phthalocyanine pigment selected from c.i. pigment blue 15:3 and c.i. pigment blue 15: 4. Further, by using a material containing 50% or more of the phthalocyanine pigment as a colorant and by containing 0.1 to 10% by mass of the ultraviolet absorber in the total solid content of the photosensitive resin composition, a cured film having excellent light resistance and capable of suppressing color mixing with pixels of other hues can be formed.

When a cured film having a thickness of 0.4 to 1.0 μm is formed, the average transmittance of light having a wavelength of 400 to 530nm in the thickness direction of the film of the photosensitive resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 85% or more. The minimum value of the transmittance of light having a wavelength of 400 to 530nm in the thickness direction of the film is preferably 40% or more, more preferably 50% or more, and still more preferably 60% or more. The average transmittance of light having a wavelength of 610 to 700nm in the thickness direction of the film is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less. The maximum value of the transmittance of light having a wavelength of 610 to 700nm in the thickness direction of the film is preferably 40% or less, more preferably 30% or less, and still more preferably 25% or less.

When a cured film having a thickness of 0.4 to 1.0 μm is formed, the photosensitive resin composition of the present invention preferably has a peak of transmittance at a wavelength of 400 to 530nm in a transmission spectrum of light having a wavelength of 400 to 700nm in a thickness direction of the film. It is preferable that the wavelength at which the transmittance reaches 50% of the peak value is present in the wavelength range of 540 to 600nm (hereinafter, this wavelength is also referred to as λ)^T50). Preferably, the wavelength of the light having a transmittance of 20% of the peak value is present in the wavelength range of 560 to 620nm (hereinafter, this wavelength is also referred to as λ)^T20)。λ^T50Preferably, the wavelength is in the range of 545 to 595nm, and more preferably in the range of 550 to 590 nm. Lambda [ alpha ]^T20Preferably in the wavelength range of 565 to 615nm, more preferably in the wavelength range of 560 to 610 nm. And, λ^T20And λ^T50Difference between (λ)^T20-λ^T50) Preferably 5 to 80nm, more preferably 7 to 50nm, and still more preferably 10 to 30 nm.

The transmittance value of the obtained cured film can be appropriately adjusted by changing the content of at least 1 phthalocyanine pigment selected from c.i. pigment blue 15:3 and c.i. pigment blue 15:4 contained in the colorant, the content of the colorant in the photosensitive resin composition, and the like.

The photosensitive resin composition of the present invention can be preferably used as a photosensitive resin composition for forming pixels of a color filter, and can be more preferably used as a photosensitive resin composition for forming cyan pixels of a color filter.

The photosensitive resin composition of the present invention can be preferably used as a photosensitive resin composition for an image display device. More specifically, the photosensitive resin composition for forming pixels can be preferably used as a color filter for an image display device, and more preferably used as a photosensitive resin composition for forming cyan pixels of a color filter for an image display device. The type of the image display device is not particularly limited, but examples thereof include a display device such as an organic electroluminescence display device having an organic semiconductor element as a light source.

The photosensitive resin composition of the present invention can also be used as a photosensitive resin composition for a solid-state imaging device. More specifically, the photosensitive resin composition for forming a pixel can be preferably used as a color filter for a solid-state imaging device, and more preferably used as a cyan photosensitive resin composition for a color filter for a solid-state imaging device.

The thickness of the cured film and the pixel formed from the photosensitive resin composition of the present invention is preferably 0.5 to 3.0. mu.m. The lower limit is preferably 0.8 μm or more, more preferably 1.0 μm or more, and further preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, and still more preferably 1.8 μm or less. The line width (pattern size) of the pixel formed by the photosensitive resin composition of the present invention is preferably 2.0 to 10.0 μm. The upper limit is preferably 7.5 μm or less, more preferably 5.0 μm or less, and still more preferably 4.0 μm or less. The lower limit is preferably 2.25 μm or more, more preferably 2.5 μm or more, and further preferably 2.75 μm or more.

The photosensitive resin composition of the present invention will be described in detail below.

Coloring agent

The photosensitive resin composition of the present invention contains a colorant. The colorant used in the photosensitive resin composition of the present invention contains at least 1 phthalocyanine pigment selected from c.i. pigment blue 15:3 and c.i. pigment blue 15: 4. Hereinafter, c.i. pigment blue 15:3 and c.i. pigment blue 15:4 are also collectively referred to as specific phthalocyanine pigments.

The average secondary particle size of the specific phthalocyanine pigment is preferably 50 to 100nm, because the cured film having spectral characteristics suitable for cyan can be easily obtained by improving the visible light transmittance. The lower limit is preferably 55nm or more, and more preferably 60nm or more, from the viewpoint of light resistance. From the viewpoint of spectral characteristics, the upper limit is preferably 95nm or less, and more preferably 90nm or less.

In the present specification, the average secondary particle diameter of the pigment is measured by directly measuring the size of the secondary particles of the pigment from an electron micrograph using a Transmission Electron Microscope (TEM). Specifically, the minor axis diameter and major axis diameter of the secondary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment. Next, for each of the 100 pigments, the volume of each pigment was determined as a cube close to the determined particle diameter, and the volume average particle diameter was defined as the average secondary particle diameter.

The colorant used in the photosensitive resin composition of the present invention contains 50 mass% or more of the specific phthalocyanine pigment, preferably 55 mass% or more of the specific phthalocyanine pigment, more preferably 60 mass% or more of the specific phthalocyanine pigment, and further preferably 65 mass% or more of the specific phthalocyanine pigment. The upper limit may be 100 mass%, 95 mass% or less, or 90 mass% or less.

The colorant used in the photosensitive resin composition of the present invention may be a colorant containing both of c.i. pigment blue 15:3 and c.i. pigment blue 15:4 as a specific phthalocyanine pigment, or may contain only one of them. When the photosensitive resin composition of the present invention contains c.i. pigment blue 15:3, the coatability of the photosensitive resin composition can be easily improved. When the photosensitive resin composition of the present invention contains c.i. pigment blue 15:4, the storage stability of the photosensitive resin composition and the heat resistance of the cured film obtained are easily improved. When the colorant used in the photosensitive resin composition of the present invention contains c.i. pigment blue 15:3 and c.i. pigment blue 15:4, the mass ratio of c.i. pigment blue 15:3 to c.i. pigment blue 15:4 is preferably 10 to 1000 parts by mass, more preferably 25 to 400 parts by mass, and still more preferably 50 to 200 parts by mass of c.i. pigment blue 15:4 with respect to 100 parts by mass of c.i. pigment blue 15: 3.

The colorant used in the photosensitive resin composition of the present invention may contain a colorant (hereinafter, also referred to as another colorant) other than the specific phthalocyanine pigment. When other colorants are contained, more excellent light resistance and an effect of improving color separation from pixels of other colors can be expected. When the colorant used in the photosensitive resin composition of the present invention further contains another colorant, the content of the other colorant in the colorant is preferably less than 50% by mass, more preferably less than 45% by mass, still more preferably less than 40% by mass, still more preferably less than 35% by mass, and particularly preferably less than 30% by mass. The lower limit is preferably 10% by mass or more, and more preferably 20% by mass or more.

The colorant used in the photosensitive resin composition of the present invention is also preferably substantially free of other colorants. According to this aspect, the light transmission amount can be increased, and a pixel with higher sensitivity can be obtained. The case where the colorant does not substantially contain another colorant means that the content of another colorant in the colorant is less than 0.5% by mass, preferably less than 0.1% by mass, and more preferably does not contain another colorant.

Examples of the other colorant include color colorants such as a red colorant, a green colorant, a blue colorant, a yellow colorant, a violet colorant, and an orange colorant, and green colorant, blue colorant, and yellow colorant are preferable, and yellow colorant is more preferable because more excellent light resistance can be easily obtained. Other colorants may be pigments or dyes. Pigments and dyes may be used in combination. The pigment may be any of an inorganic pigment and an organic pigment. In addition, as the pigment, a material in which a part of the inorganic pigment or the organic-inorganic pigment is substituted with an organic color developing group can be used. By partially substituting the inorganic pigment or the organic-inorganic pigment with the organic chromophore, hue design can be easily performed. Examples of the pigment include the following pigments.

Pigment yellow 1,2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35:1, 36:1, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 215, 231, 213, and 233 (yellow) series pigments (yellow-series) and the like,

Pigment orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (orange pigment above),

Pigment Red 1,2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, 294 (xanthene series, Organo, Ultrash series 296), Bluish series (295) and even or even (azo series) pigments such as azo series pigments,

C.I. pigment Green 7, 10, 36, 37, 58, 59, 62, 63, etc. (above: Green pigment),

C.I. pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane-based) or 61 (xanthene-based) (the above is a violet pigment),

C.i. pigment blue 1,2, 15:1, 15:2, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo system), 88 (methine system), etc. (the above is a blue pigment).

Furthermore, as the green pigment, a zinc halide phthalocyanine pigment having 10 to 14 halogen atoms, 8 to 12 bromine atoms and 2 to 5 chlorine atoms on average in 1 molecule can be used. Specific examples thereof include the compounds described in International publication No. 2015/118720. Further, as the green pigment, a compound described in the specification of chinese patent application No. 106909027, a phthalocyanine compound having a phosphate as a ligand described in international publication No. 2012/102395, a phthalocyanine compound described in japanese patent application laid-open No. 2019-008014, and a phthalocyanine compound described in japanese patent application laid-open No. 2018-180023 can be used.

Further, as the blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples thereof include compounds described in paragraphs 0022 to 0030 of Japanese patent application laid-open No. 2012 and 247591 and paragraph 0047 of Japanese patent application laid-open No. 2011 and 157478.

Further, as the yellow pigment, a compound described in Japanese patent laid-open publication No. 2017-201003, a compound described in Japanese patent laid-open publication No. 2017-197719, a compound described in paragraphs 0011 to 0062 and 0137 to 0276 of Japanese patent laid-open publication No. 2017-171912, a compound described in paragraphs 0010 to 0062 and 0138 to 0295 of Japanese patent laid-open publication No. 2017-171913, a compound described in paragraphs 0011 to 0060192 and 0139 to 0270 of Japanese patent laid-open publication No. 2017-171914, a compound described in paragraphs 0010 to 0065 and 0142 to 0222 of Japanese patent laid-open publication No. 2017-171914, a phthalone compound described in paragraphs 0011 to 0034 of Japanese patent laid-open publication No. 2013-054339, a quinophthalone compound described in paragraphs 0013 to 0058 and a quinophthalone compound described in paragraphs 2014-026228, and an isoindoline compound described in paragraphs 644 and 2018 of Japanese patent laid-open publication No. 2013, The quinophthalone compound described in Japanese patent laid-open publication No. 2018-203798, the quinophthalone compound described in Japanese patent laid-open publication No. 2018-062578, the quinophthalone compound described in Japanese patent laid-open publication No. 6432077, the quinophthalone compound described in Japanese patent laid-open publication No. 6432076, the quinophthalone compound described in Japanese patent laid-open publication No. 2018-155881, the quinophthalone compound described in Japanese patent laid-open publication No. 2018-111757, the quinophthalone compound described in Japanese patent laid-open publication No. 2018-040835, the quinophthalone compound described in Japanese patent laid-open publication No. 2017-197640, the quinophthalone compound described in Japanese patent laid-open publication No. 2016-145282, the quinophthalone compound described in Japanese patent laid-open publication No. 2014085565, the quinophthalone compound described in Japanese patent laid-open publication No. 2014-021139, The quinophthalone compound described in Japanese patent application laid-open No. 2013-209614, the quinophthalone compound described in Japanese patent application laid-open No. 2013-209435, the quinophthalone compound described in Japanese patent application laid-open No. 2013-181015, the quinophthalone compound described in Japanese patent application laid-open No. 2013-061622, the quinophthalone compound described in Japanese patent application laid-open No. 2013-054339, the quinophthalone compound described in Japanese patent application laid-open No. 2013-032486, the quinophthalone compound described in Japanese patent application laid-open No. 2012-226110, the quinophthalone compound described in Japanese patent application laid-open No. 2008-074987, the quinophthalone compound described in Japanese patent application laid-open No. 2008-081565, the quinophthalone compound described in Japanese patent application laid-open No. 2008-074986, the quinophthalone compound described in Japanese patent application laid-open No. 2008-074985, The quinophthalone compound described in Japanese patent application laid-open No. 2008-050420, the quinophthalone compound described in Japanese patent application laid-open No. 2008-031281, the quinophthalone compound described in Japanese patent application laid-open No. 48-032765, the quinophthalone compound described in Japanese patent application laid-open No. 2019-008014, the compound represented by the following formula (QP1), and the compound represented by the following formula (QP 2).

[ chemical formula 1]

In formula (QP1), X¹～X¹⁶Each independently represents a hydrogen atom or a halogen atom, Z¹Represents an alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by the formula (QP1) include the compounds described in paragraph 0016 of japanese patent No. 6443711.

[ chemical formula 2]

In formula (QP2), Y¹～Y³Each independently represents a halogen atom. n and m are integers of 0 to 6, and p is an integer of 0 to 5. (n + m) is 1 or more. Specific examples of the compound represented by the formula (QP2) include compounds described in paragraphs 0047 to 0048 of Japanese patent No. 6432077.

As the red pigment, a diketopyrrolopyrrole compound described in Japanese patent laid-open No. 2017-201384 in which at least 1 bromine atom is substituted in the structure, a diketopyrrolopyrrole compound described in paragraphs 0016 to 0022 of Japanese patent No. 6248838, a diketopyrrolopyrrole compound described in International publication No. 2012/102399, a diketopyrrolopyrrole compound described in International publication No. 2012/117965, a naphthol azo compound described in Japanese patent laid-open No. 2012-229344, and the like can be used. As the red pigment, a compound having a structure in which an aromatic ring group obtained by introducing a group to which an oxygen atom, a sulfur atom, or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton can be used.

The dye is not particularly limited, and a known dye can be used. Examples thereof include dyes such as pyrazole azo-based, anilino azo-based, triarylmethane-based, anthraquinone-based, anthrapyridone quinone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes. Furthermore, thiazole compounds described in Japanese patent laid-open No. 2012 and 158649, azo compounds described in Japanese patent laid-open No. 2011 and 184493, and azo compounds described in Japanese patent laid-open No. 2011 and 145540 can be preferably used. Further, as the yellow dye, a quinophthalone compound described in paragraphs 0011 to 0034 of Japanese patent application laid-open No. 2013-054339, a quinophthalone compound described in paragraphs 0013 to 0058 of Japanese patent application laid-open No. 2014-026228, or the like can be used.

Other colorants can be pigment multimers. The pigment multimer has two or more pigment structures, preferably three or more pigment structures, in one molecule. The upper limit is not particularly limited, but may be 100 or less. The plurality of pigment structures in one molecule may be the same pigment structure or different pigment structures. The weight average molecular weight (Mw) of the pigment polymer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and still more preferably 6000 or more. The upper limit is more preferably 30000 or less, and still more preferably 20000 or less. The dye multimer can also be a compound described in Japanese patent application laid-open Nos. 2011-213925, 2013-041097, 2015-028144, 2015-030742, or International publication No. 2016/031442.

The content of the colorant in the total solid content of the photosensitive resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less.

Resin

The photosensitive resin composition of the present invention contains a resin. The resin is blended for use in dispersing particles such as a pigment in the composition or for use in a binder, for example. The resin used mainly for dispersing the particles and the like in the composition is also referred to as a dispersant. However, these uses of the resin are examples, and the resin may be used for purposes other than these uses.

Examples of the resin include (meth) acrylic resins, (meth) acrylamide resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenyl resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, silicone resins, polyimide resins, and polyurethane resins.

The weight average molecular weight (Mw) of the resin is preferably 2000 to 2000000. The upper limit is preferably 1000000 or less, more preferably 500000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and further preferably 5000 or more.

The photosensitive resin composition of the present invention also preferably contains a resin having an amine value. According to this embodiment, the pigment can be finely dispersed, and even when a fine pixel (pattern) is formed using the photosensitive resin composition, a pixel (pattern) with few defects can be formed. The amine value of the resin is preferably 25 to 60mgKOH/g, more preferably 26 to 59mgKOH/g, and still more preferably 27 to 58 mgKOH/g. A resin having an amine value is preferably used as a dispersant for the above-mentioned specific phthalocyanine pigment.

The acid value of the resin having an amine value is preferably 0 to 250mgKOH/g from the viewpoint of achieving both the resolution of the photosensitive resin composition and the dispersibility of the pigment. The upper limit is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less. The lower limit is preferably 5mgKOH/g or more, more preferably 10mgKOH/g or more, from the viewpoint of enhancing the alkali solubility and facilitating the resolution enhancement. Also, the acid value of the resin having an amine value may be 0 mgKOH/g. When the acid value of the resin having an amine value is 0mgKOH/g, an effect of improving the dispersion stability of the pigment can be obtained.

The number average molecular weight of the resin having an amine value is preferably 500 to 50000, more preferably 3000 to 30000.

Examples of the resin having an amine value include a (meth) acrylic resin, a polyimide resin, a polyester resin, a polyether resin, and a polyamide resin, and the (meth) acrylic resin is preferable because the resin has good transparency and heat resistance. Specific examples of the basic resin include a vinyl monomer containing an N, N-disubstituted amino group, a copolymer of an alkyl (meth) acrylate monomer and another vinyl monomer, and the like. Examples of the vinyl monomer containing an N, N-disubstituted amino group include N, N-dimethylamino ethyl (meth) acrylate, N-diethylamino ethyl (meth) acrylate, N-dimethylamino propyl (meth) acrylate, N-diethylamino propyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylamide, N-diethylaminoethyl (meth) acrylamide, and the like. Examples of the alkyl (meth) acrylate monomer include (meth) acrylates obtained by a reaction of an unsaturated monocarboxylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate or lauryl (meth) acrylate with an alkyl alcohol having 1 to 18 carbon atoms. Examples of the other vinyl monomers include nitro-containing vinyl monomers such as (meth) acrylonitrile, vinyl aromatic monomers such as styrene, α -methylstyrene or benzyl (meth) acrylate, hydroxyl-containing vinyl monomers such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate or polyethylene glycol (meth) acrylate, amide-containing vinyl monomers such as (meth) acrylamide, N-dimethylacrylamide, N-isopropylacrylamide or diacetoneacrylamide, vinyl monomers such as N-methylol (meth) acrylamide or dimethylol (meth) acrylamide, alkoxymethyl-containing vinyl monomers such as N-methoxymethyl (meth) acrylamide or N-butoxymethyl (meth) acrylamide, and the like, Olefins such as ethylene, propylene and isoprene, dienes such as chloroprene and butadiene, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether, and fatty acid vinyl esters such as vinyl acetate and vinyl propionate.

Examples of commercially available products of resins having an amine value include DISPERBYK161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (manufactured by BYK Japan k. above), solpperse 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (manufactured by Lubrizol Japan limited. above), Efka PX 4300, 4330, 4046, 4060, 4080 (manufactured by BASF corporation above), and the like.

The photosensitive resin composition of the present invention preferably contains an alkali-soluble resin. The photosensitive resin composition of the present invention contains an alkali-soluble resin, whereby the developability of the photosensitive resin composition can be improved, and the generation of development residue and the like can be effectively suppressed when a pattern is formed by photolithography using the photosensitive resin composition of the present invention. Examples of the alkali-soluble resin include resins having an acid group. Examples of the acid group include a carboxyl group, a phosphoric group, a sulfo group, a phenolic hydroxyl group, and the like, and a carboxyl group is preferable. The kind of the acid group of the alkali-soluble resin may be only 1 kind, or may be 2 or more kinds. In addition, an alkali-soluble resin can also be used as a dispersant.

The alkali-soluble resin preferably contains a repeating unit having an acid group on a side chain, and more preferably contains 5 to 70 mol% of a repeating unit having an acid group on a side chain among all repeating units of the resin. The upper limit of the content of the repeating unit having an acid group in a side chain is preferably 50 mol% or less, and more preferably 30 mol% or less. The lower limit of the content of the repeating unit having an acid group in a side chain is preferably 10 mol% or more, and more preferably 20 mol% or more.

The alkali-soluble resin is also preferably an alkali-soluble resin having a polymerizable group. Examples of the polymerizable group include a (meth) allyl group and a (meth) acryloyl group. The alkali-soluble resin having a polymerizable group is preferably a resin containing a repeating unit having a polymerizable group on a side chain and a repeating unit having an acid group on a side chain.

The alkali-soluble resin also preferably contains a repeating unit derived from a monomer component containing a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds are sometimes also referred to as "ether dimer").

[ chemical formula 3]

In the formula (ED1), R¹And R²Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

[ chemical formula 4]

In the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. The formula (ED2) can be described in detail in Japanese patent application laid-open No. 2010-168539, which is incorporated herein by reference.

As a specific example of the ether dimer, for example, reference can be made to the description in paragraph 0317 of Japanese patent application laid-open No. 2013-029760, the contents of which are incorporated herein by reference.

As for the alkali-soluble resin, reference can be made to the descriptions in paragraphs 0558 to 0571 of Japanese patent application laid-open No. 2012 and 208494 (paragraphs 0685 to 0700 of the corresponding US patent application laid-open No. 2012/0235099), paragraphs 0076 to 0099 of Japanese patent application laid-open No. 2012 and 198408, and descriptions of Japanese patent application laid-open No. 2018 and 105911, which are incorporated herein by reference.

The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH/g. The lower limit is preferably 50mgKOH/g or more, more preferably 70mgKOH/g or more. The upper limit is preferably 400mgKOH/g or less, more preferably 300mgKOH/g or less, and still more preferably 200mgKOH/g or less.

In the photosensitive resin composition of the present invention, a resin having a maleimide structure can be used as the resin. In the present specification, the maleimide structure refers to a structure derived from a maleimide compound. Examples of the maleimide compound include maleimide and N-substituted maleimide. Examples of the N-substituted maleimide include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, N-butylmaleimide, and laurylmaleimide.

The resin having a maleimide structure is preferably a resin containing a repeating unit having a maleimide structure. The maleimide structure may be contained in the main chain of the repeating unit or may be contained in the side chain of the repeating unit. The maleimide structure is preferably contained in the main chain of the repeating unit from the viewpoint of the easiness of forming a cured film in which color unevenness is suppressed.

The photosensitive resin composition of the present invention also preferably contains a resin I (hereinafter, also referred to as a resin I) containing, as a resin, a repeating unit derived from a compound represented by the formula (I) (hereinafter, also referred to as a repeating unit I1-1). By containing the resin i in the photosensitive resin composition of the present invention, a cured film in which color unevenness is suppressed can be easily obtained. The content of the repeating unit i1-1 in all the repeating units of the resin i is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more.

[ chemical formula 5]

In the formula, Xi¹Represents O or NH, preferably O.

Ri¹Represents a hydrogen atom or a methyl group.

Li¹Represents a 2-valent linking group. As the linking group having a valence of 2, there may be mentioned hydrocarbon groups, heterocyclic groups, -NH-, -SO-, -SO₂-, -CO-, -O-, -COO-, -OCO-, -S-, and a combination of two or more of these. Examples of the hydrocarbon group include an alkyl group and an aryl group. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Examples of the hetero atom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, a sulfur atom and the like. The number of hetero atoms constituting the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a single ring or a condensed ring. The hydrocarbon group and the heterocyclic group may have a substituent. Examples of the substituent include an alkyl group, an aryl group, a hydroxyl group, a halogen atom, and the like.

Ri¹⁰Represents a substituent. As Ri¹⁰The substituent represented is a substituent Ti shown below, preferably a hydrocarbon group, and more preferably an alkyl group which may have an aryl group as a substituent.

m represents an integer of 0 to 2, preferably 0 or 1, more preferably 0.

p represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 3, further preferably 0 to 2, further preferably 0 or 1, and particularly preferably 1.

(substituent Ti)

Examples of the substituent Ti include a halogen atom, a cyano group, a nitro group, a hydrocarbon group, a heterocyclic group and-ORti¹、-CORti¹、-COORti¹、-OCORti¹、-NRti¹Rti²、-NHCORti¹、-CONRti¹Rti²、-NHCONRti¹Rti²、-NHCOORti¹、-SRti¹、-SO₂Rti¹、-SO₂ORti¹、-NHSO₂Rti¹or-SO₂NRti¹Rti²。Rti¹And Rti²Each independently represents a hydrogen atom, a hydrocarbon group or a heterocyclic group. Rti¹And Rti²May be bonded to form a ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 15, and still more preferably 1 to 8. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched, and more preferably branched.

The number of carbon atoms of the alkenyl group is preferably 2 to 30, more preferably 2 to 12, and particularly preferably 2 to 8. The alkenyl group may be linear, branched or cyclic, and is preferably linear or branched.

The number of carbon atoms of the alkynyl group is preferably 2 to 30, more preferably 2 to 25. The alkynyl group may be any of linear, branched and cyclic, and is preferably linear or branched.

The number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12.

The heterocyclic group may be a single ring or a condensed ring. The heterocyclic group is preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 4. The number of hetero atoms constituting the ring of the heterocyclic group is preferably 1 to 3. The hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12.

The hydrocarbon group and the heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described above for the substituent Ti.

The compound represented by the formula (I) is preferably a compound represented by the following formula (I-1).

[ chemical formula 6]

Xi¹Represents O or NH, preferably O.

Ri¹Represents a hydrogen atom or a methyl group.

Ri²、Ri³And Ri¹¹Each independently represents a hydrocarbon group.

Ri²And Ri³The hydrocarbon group represented is preferably an alkylene group or an arylene group, and more preferably an alkylene group. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 or 3. Ri¹¹The hydrocarbon group represented is preferably an alkyl group which may have an aryl group as a substituent, and more preferably an alkyl group having an aryl group as a substituent. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5. The number of carbon atoms of an alkyl group when the alkyl group has an aryl group as a substituent means the number of carbon atoms of the alkyl moiety.

Ri¹²Represents a substituent. As Ri¹²Examples of the substituent include the substituent Ti described above.

n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and further preferably an integer of 0 to 3.

m represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

p1 represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 3, further preferably 0 to 2, further preferably 0 to 1, and particularly preferably 0.

q1 represents an integer of 1 or more, preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2, and particularly preferably 1.

The compound represented by the formula (I) is preferably a compound represented by the following formula (III).

[ chemical formula 7]

In the formula, Ri¹Represents a hydrogen atom or a methyl group, Ri²¹And Ri²²Each independently represents an alkylene group, and n represents an integer of 0 to 15. Ri²¹And Ri²²The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 or 3. n is preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and further preferably an integer of 0 to 3.

Examples of the compound represented by the formula (I) include (meth) acrylates modified with ethylene oxide or propylene oxide of p-cumylphenol. Examples of commercially available products include ARONIX M-110 (manufactured by TOAGOSEI CO., LTD.).

The resin i preferably further contains a repeating unit derived from an alkyl (meth) acrylate (hereinafter also referred to as repeating unit i 1-2). When the resin i further has the repeating unit i1-2, an effect of improving the solvent solubility of the photosensitive resin composition can be obtained. The alkyl group of the alkyl (meth) acrylate preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and still more preferably 3 to 6 carbon atoms. Preferred specific examples of the alkyl (meth) acrylate include n-butyl (meth) acrylate, ethyl (meth) acrylate, and 2-ethylhexyl acrylate, and n-butyl (meth) acrylate is preferred because it is easy to obtain more excellent solvent solubility. The content of the repeating unit i1-2 in all the repeating units of the resin i is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more.

The resin i preferably further contains a repeating unit having an acid group. According to this embodiment, the effect of improving the developability of the photosensitive resin composition can be obtained. The content of the repeating unit having an acid group in all the repeating units of the resin i is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more. The upper limit is preferably 60 mol% or less, and more preferably 50 mol% or less. The resin i containing a repeating unit having an acid group may also be an alkali-soluble resin.

The resin i preferably further contains a repeating unit having an ethylenically unsaturated bond-containing group. The content of the repeating unit having an ethylenically unsaturated bond-containing group in all the repeating units of the resin i is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more. The upper limit is preferably 50 mol% or less, and more preferably 40 mol% or less.

The photosensitive resin composition of the present invention also preferably contains a resin having an aromatic carboxyl group (hereinafter, also referred to as a resin Ac). By using the resin Ac, a cured film which is less likely to cause fading of the pigment during development and has excellent developability can be formed.

In the resin Ac, the aromatic carboxyl group may be contained in the main chain of the repeating unit or in the side chain of the repeating unit. The aromatic carboxyl group is preferably contained in the main chain of the repeating unit for the reason that the above-mentioned effects can be more remarkably obtained. Although not specifically shown in detail, it is presumed that these properties can be further improved by the presence of an aromatic carboxyl group in the vicinity of the main chain. In the present specification, an aromatic carboxyl group means a group having a structure in which 1 or more carboxyl groups are bonded to an aromatic ring. In the aromatic carboxyl group, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, more preferably 1 to 2.

The resin Ac is preferably a resin containing at least one repeating unit selected from the group consisting of a repeating unit represented by the formula (b-1) and a repeating unit represented by the formula (b-10).

[ chemical formula 8]

In the formula (b-1), Ar¹Represents a group containing an aromatic carboxyl group, L¹represents-COO-or-CONH-, L²Represents a 2-valent linking group.

In the formula (b-10), Ar¹⁰Represents a group containing an aromatic carboxyl group，L¹¹represents-COO-or-CONH-, L¹²Represents a linking group having a valence of 3, P¹⁰Represents a polymer chain.

First, the formula (b-1) will be explained. In the formula (b-1), Ar is contained¹Examples of the group of the aromatic carboxyl group include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, and the like. Examples of the aromatic tricarboxylic acid anhydride and the aromatic tetracarboxylic acid anhydride include compounds having the following structures.

[ chemical formula 9]

In the above formula, Q¹Represents a single bond, -O-, -CO-, -COOCH₂CH₂OCO-、-SO₂-、-C(CF₃)₂-, a group represented by the following formula (Q-1) or a group represented by the following formula (Q-2).

[ chemical formula 10]

As containing Ar¹Specific examples of the group of the aromatic carboxyl group include a group represented by the formula (Ar-1), a group represented by the formula (Ar-2), a group represented by the formula (Ar-3), and the like.

[ chemical formula 11]

In the formula (Ar-1), n1 represents an integer of 1 to 4, preferably 1 or 2, more preferably 2.

In the formula (Ar-2), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and further preferably 2.

In the formula (Ar-3), n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and still more preferably 1. Wherein at least one of n3 and n4 is an integer of 1 or more.

In the formula (Ar-3), Q¹Represents a single bond, -O-, -CO-, -COOCH₂CH₂OCO-、-SO₂-、-C(CF₃)₂-, a group represented by the above formula (Q-1) or a group represented by the above formula (Q-2).

In the formula (b-1), L¹represents-COO-or-CONH-, and preferably represents-COO-.

In the formula (b-1), as L²Examples of the 2-valent linking group include alkylene, arylene, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and a combination of 2 or more of these groups. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The alkylene group may be any of linear, branched, and cyclic. The number of carbon atoms of the arylene group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxyl group and the like. L is²The 2-valent linking group represented is preferably represented by-O-L^2a-O-represents a group. L is^2aAlkylene groups; an arylene group; a group in which an alkylene group and an arylene group are combined; and a combination of at least 1 kind selected from the group consisting of alkylene and arylene with at least 1 kind selected from the group consisting of-O-, -CO-, -COO-, -OCO-, -NH-and-S-, and the like. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The alkylene group may be any of linear, branched, and cyclic. The alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxyl group and the like.

Next, the formula (b-10) will be described. In the formula (b-10), as containing Ar¹⁰A group of an aromatic carboxyl group represented by (a) with Ar of the formula (b-1)¹The same meanings are given above, and preferred ranges are also the same.

In the formula (b-10), L¹¹represents-COO-or-CONH-, and preferably represents-COO-.

In the formula (b-10), as L¹²Examples of the 3-valent linking group include a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and a combination of two or more of these groups. Hydrocarbyl radicalExamples thereof include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms. The aliphatic hydrocarbon group may be any of linear, branched, and cyclic. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxyl group and the like. L is¹²The linking group having a valence of 3 represented is preferably a group represented by the following formula (L12-1), more preferably a group represented by the formula (L12-2).

[ chemical formula 12]

L^12aAnd L^12bEach represents a linking group having a valence of 3, X¹Represents S, 1 represents L of formula (b-10)¹¹2 represents P with formula (b-10)¹⁰The bonding position of (2).

As L^12aAnd L^12bExamples of the linking group having a valence of 3 include a hydrocarbon group; a group formed by combining a hydrocarbon group with at least 1 kind selected from the group consisting of-O-, -CO-, -COO-, -OCO-, -NH-, and-S-, and the like.

In the formula (b-10), P¹⁰Represents a polymer chain. P¹⁰The polymer chain represented preferably has at least 1 repeating unit selected from the group consisting of a poly (meth) acrylic acid repeating unit, a polyether repeating unit, a polyester repeating unit, and a polyol repeating unit. Polymer chain P¹⁰The weight average molecular weight of (2) is preferably 500 to 20000. The lower limit is preferably 1000 or more. The upper limit is preferably 10000 or less, more preferably 5000 or less, and further preferably 3000 or less. If P¹⁰When the weight average molecular weight of (2) is within the above range, the dispersibility of the pigment in the composition is good. In the case where the resin having an aromatic carboxyl group is a resin having a repeating unit represented by the formula (b-10), the resin can be preferably used as a dispersant.

The photosensitive resin composition of the present invention also preferably uses a resin having a structure represented by formula (OP1) (hereinafter, also referred to as resin OP). The resin can be preferably used as a dispersant.

[ chemical formula 13]

In the formula, Rp⁴The number average molecular weight is 400-30000, and the number average molecular weight is polyether residue and/or polyester residue containing ethylenic unsaturated bond group, y represents 1-2.

Rp⁴The number average molecular weight of (2) is more preferably 400 to 10000, still more preferably 400 to 3000. If Rp⁴When the number average molecular weight of (b) is within the above range, the dispersibility of the pigment is good, and these resins can be preferably used as a dispersant.

As Rp⁴Examples of the polyether residue and/or polyester residue having an ethylenically unsaturated bond-containing group include polyether residues and/or polyester residues having a styryl group, a (meth) acryloyl group, a cyanoacryloyl group, a vinyl ether group, and the like.

Rp⁴Preferred is a group represented by the following formula (Rp-1).

-Rp¹²-O-Rp¹³-(O-Rp¹⁴)_S

In the formula, Rp¹²Denotes alkylene, Rp¹³Denotes a polyhydric alcohol residue having a valence of 3 or more, Rp¹⁴Represents a (meth) acryloyl group or a cyanoacryloyl group, and s represents 2 or more.

Rp¹²An alkylene group having 8 or less carbon atoms is preferable. From the viewpoint of pigment dispersibility, s is preferably 2 or more. In this case, Rp¹⁴Groups different from each other may be used. Further preferably, s is 2 to 5, particularly preferably 2.

As Rp¹³Examples of the polyhydric alcohol having a valence of 3 or more include glycerin, propanol, pentaerythritol, dipentaerythritol, and the like. Particularly preferred are polyols having a valence of 3 to 6.

In the resin OP, Rp⁴May be a single phosphoric acid ester or a plurality of phosphoric acid esters having different Rp's may be used⁴And (3) a phosphate ester. And, the resin OP may be only a resin in which y in the formula (OP1) is 1,or a mixture of a resin in which y is 1 in formula (OP1) and a resin in which y is 2 in formula (OP 1). And, if Rp of the compound represented by the formula (OP1)⁴The polycaprolactone residue having a number average molecular weight of 400 to 10000 (more preferably 400 to 3000) is preferable because the pigment dispersibility is good.

The photosensitive resin composition of the present invention may contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) means a resin having an acid group in an amount larger than that of a basic group. The acid dispersant (acidic resin) is preferably a resin having an acid group content of 70 mol% or more, where the total amount of the acid group and the base group is 100 mol%. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. The basic dispersant (basic resin) is a resin having a base group in an amount larger than that of an acid group. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of the acid groups and the base groups is 100 mol%. The basic group of the basic dispersant is preferably an amino group.

The resin used as the dispersant is preferably a resin having the above-mentioned amine value.

The resin used as a dispersant is also preferably a graft resin. The details of the graft resin can be found in paragraphs 0025 to 0094 of Japanese patent application laid-open No. 2012 and 255128, which are incorporated herein by reference.

The resin used as the dispersant is also preferably a polyimide-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimide-based dispersant is preferably a resin having a main chain and a side chain, wherein the main chain has a partial structure having a functional group with a pKa of 14 or less, and the side chain has 40 to 10000 in number of atoms, and has a basic nitrogen atom at least at one position of the main chain and the side chain. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. The polyimide-based dispersant can be described in paragraphs 0102 to 0166 of Japanese patent application laid-open No. 2012 and 255128, the contents of which are incorporated herein by reference.

The resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core portion. Examples of such a resin include dendrimers (including star polymers). Specific examples of the dendrimer include the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese patent laid-open publication No. 2013-043962.

The resin used as the dispersant is also preferably a resin having a repeating unit having an ethylenically unsaturated bond-containing group on a side chain. The content of the repeating unit having an ethylenically unsaturated bond-containing group in a side chain among all the repeating units of the resin is preferably 10 mol% or more, more preferably 10 to 80 mol%, and further preferably 20 to 70 mol%. Further, as the dispersant, a resin described in Japanese patent application laid-open No. 2018-087939 can be used.

The dispersant is also available as a commercially available product, and specific examples thereof include DISPERBYK series manufactured by BYK Japan K.K., SOLSPERSE series manufactured by Lubrizol Japan Limited, Efka series manufactured by BASF, Ajinomoto Fine-Technio Co., Inc., AJISPER series manufactured by Inc. Further, the products described in paragraph 0129 of Japanese patent laid-open Nos. 2012 and 137564 and 0235 of Japanese patent laid-open Nos. 2017 and 194662 can also be used as the dispersing agent.

The content of the resin in the total solid content of the photosensitive resin composition is preferably 10 to 50 mass%. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less. The lower limit is preferably 15% by mass or more, and more preferably 20% by mass or more.

The content of the alkali-soluble resin in the resin contained in the photosensitive resin composition of the present invention is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and still more preferably 30 to 100% by mass.

The content of the resin having an amine value in the resin contained in the photosensitive resin composition of the present invention is preferably 0 to 100% by mass. The upper limit is preferably 90% by mass or less, and more preferably 80% by mass or less. The lower limit is preferably 10% by mass or more, and more preferably 20% by mass or more.

When the photosensitive resin composition of the present invention contains a dispersant as a resin, the content of the dispersant is preferably 10 to 100 parts by mass per 100 parts by mass of the specific phthalocyanine pigment. The upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less. The lower limit is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more. The content of the resin having an amine value in the dispersant is preferably 0 to 100% by mass, more preferably 10 to 100% by mass, and still more preferably 20 to 100% by mass. The content of the dispersant in the resin is preferably 10 to 100% by mass. The upper limit is preferably 95% by mass or less, and more preferably 90% by mass or less. The lower limit is preferably 20% by mass or more, and more preferably 30% by mass or more.

(polymerizable Compound)

The photosensitive resin composition of the present invention contains a polymerizable compound. As the polymerizable compound, a known compound that can be crosslinked by a radical, an acid, or heat can be used. In the present invention, the polymerizable compound is preferably a compound having an ethylenically unsaturated bond-containing group, for example. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, (meth) allyl group, and (meth) acryloyl group. The polymerizable compound used in the present invention is preferably a radical polymerizable compound.

The polymerizable compound may be any of monomers, prepolymers, oligomers, and other chemical forms, and is preferably a monomer. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is preferably 2000 or less, more preferably 1500 or less, and still more preferably 1000 or less. The lower limit is preferably 150 or more, more preferably 250 or more.

The ethylenically unsaturated group-containing group (hereinafter referred to as C value) of the monomeric polymerizable compound is preferably 2 to 14mmol/g from the viewpoints of the stability of the photosensitive resin composition over time, the light resistance of the cured film obtained, and the like. The lower limit is preferably 3mmol/g or more, more preferably 4mmol/g or more, and still more preferably 5mmol/g or more. The upper limit is preferably 12mmol/g or less, more preferably 10mmol/g or less, and still more preferably 8mmol/g or less. The value of C ═ C of the ethylenically unsaturated bond-containing group is calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in 1 molecule of the ethylenically unsaturated bond-containing group by the molecular weight of the polymerizable compound.

The polymerizable compound is preferably a compound having 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound having 3 to 15 ethylenically unsaturated bond-containing groups, and still more preferably a compound having 3 to 6 ethylenically unsaturated bond-containing groups. The polymerizable compound is preferably a 3-15 functional (meth) acrylate compound, and more preferably a 3-6 functional (meth) acrylate compound. Specific examples of the polymerizable compound include those described in paragraphs 0095 to 0108 of Japanese patent laid-open No. 2009-288705, 0227 of Japanese patent laid-open No. 2013-029760, 0254 to 0257 of Japanese patent laid-open No. 2008-292970, 0034 to 0038 of Japanese patent laid-open No. 2013-253224, 0477 of Japanese patent laid-open No. 2012-208494, Japanese patent laid-open No. 2017-048367, Japanese patent No. 6057891, Japanese patent No. 6031807, and Japanese patent laid-open No. 2017-194662, which are incorporated herein by reference.

As the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330, available as a commercial product; Nippon Kayaku co., ltd., manufactured by ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320, available as a commercial product; Nippon Kayaku co., manufactured by ltd.), dipentaerythritol penta (meth) acrylate (KAYARAD D-310, available as a commercial product; Nippon Kayaku co., manufactured by ltd.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA, available as a commercial product; Nippon Kayaku co., ltd., manufactured by NK ESTER a-DPH-12E; Shin-Nakamura co., manufactured by ltd., and a compound having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and/or propylene glycol residues (e.g., SR454, SR499, manufactured by sarcompany, inc., manufactured by. Further, as the polymerizable compound, diglycerol EO (ethylene oxide) -modified (meth) acrylate (M-460; TOAGOSEI CO., LTD., manufactured by Kogyo Co., Ltd.), pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd., NK ESTER A-TMMT), 1, 6-hexanediol diacrylate (Nippon Kayaku Co., manufactured by Ltd., KAYARAD HDDA), RP-1040(Nippon Kayaku Co., Ltd., manufactured by Ltd.), ARONIX TO-2349(TOAGOSEI CO., LTD., manufactured by Kogyo UA-7200(Shin-Nakamura Chemical., manufactured by Ltd.), 8UH-1006, 8UH-1012(TAISEI FINE CHEMICAL CO., LTD., manufactured by LTD.), LIGHT YEPOYEPOBB-A0 (OEKYISHA CO., LTD., manufactured by Kogyo., LTD., and the like) can be used.

Also, as the polymerizable compound, a 3-functional (meth) acrylate compound such as trimethylolpropane tri (meth) acrylate, trimethylolpropane-propylene oxide-modified tri (meth) acrylate, trimethylolpropane-ethylene oxide-modified tri (meth) acrylate, isocyanuric acid-ethylene oxide-modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, or the like is preferably used. Commercially available products of 3-functional (meth) acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, M-450 (manufactured by TOAGOSEI CO., LTD.), NK ESTER A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (Shin-Nakamura Chemical Co., manufactured by Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd., manufactured).

The polymerizable compound having an acid group can be used. By using a polymerizable compound having an acid group, the polymerizable compound in the unexposed portion can be easily removed during development, and the generation of development residue can be suppressed. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and a carboxyl group is preferable. Commercially available products of polymerizable compounds having an acid group include ARONIX M-305, M-510, M-520, and ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.). The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40mgKOH/g, more preferably 5 to 30 mgKOH/g. When the acid value of the polymerizable compound is 0.1mgKOH/g or more, the solubility in a developer is good, and when it is 40mgKOH/g or less, the production and handling are facilitated.

As the polymerizable compound, a polymerizable compound having a caprolactone structure can be used. The polymerizable compound having a caprolactone structure is commercially available as KAYARAD DPCA series from Nippon Kayaku Co., Ltd. and includes DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.

The polymerizable compound having an alkyleneoxy group can be used. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and/or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and still more preferably a 3-6 functional (meth) acrylate compound having 4-20 ethyleneoxy groups. Examples of commercially available products of the polymerizable compound having an alkyleneoxy group include 4-functional (meth) acrylate SR-494 having 4 ethyleneoxy groups and 3-functional (meth) acrylate KAYARAD TPA-330 having 3 isobutyleneoxy groups, which are manufactured by SARTOMER Company, inc.

As the polymerizable compound, a polymerizable compound having a fluorene skeleton can be used. Commercially available products of polymerizable compounds having a fluorene skeleton include OGSOL EA-0200 and EA-0300 (a (meth) acrylate monomer having a fluorene skeleton, manufactured by Osaka Gas Chemicals co., ltd.).

As the polymerizable compound, a compound substantially free of environmental control substances such as toluene is also preferably used. Commercially available products of these compounds include KAYARAD DPHA LT and KAYARAD DPEA-12LT (manufactured by Nippon Kayaku Co., Ltd.).

As the polymerizable compound, urethane acrylates as described in Japanese patent publication No. 48-041708, Japanese patent publication No. 51-037193, Japanese patent publication No. 02-032293 and Japanese patent publication No. 02-016765; urethane compounds having an ethylene oxide skeleton as described in Japanese patent publication No. 58-049860, Japanese patent publication No. 56-017654, Japanese patent publication No. 62-039417 and Japanese patent publication No. 62-039418. It is also preferable to use polymerizable compounds having an amino structure or a thioether structure in the molecule as described in Japanese patent application laid-open Nos. 63-277653, 63-260909 and 01-105238. Further, commercially available compounds such as UA-7200(Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, and LINC-202UA (KYOEISHA CHEMICAL CO., LTD.) can be used as the polymerizable compound.

The content of the polymerizable compound in the total solid content of the photosensitive resin composition is preferably 0.1 to 50% by mass. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 45% by mass or less, and still more preferably 40% by mass or less. The polymerizable compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When 2 or more kinds are used in combination, the total amount of them is preferably within the above range.

[ photopolymerization initiator ]

The photosensitive resin composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light in the ultraviolet region to the visible region is preferable. The photopolymerization initiator is preferably a photo radical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, and the like), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α -hydroxyketone compounds, α -aminoketone compounds, and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyl triazine (trihalomethyl triazine) compound, a benzyldimethyl ketal compound, an α -hydroxy ketone compound, an α -amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound, more preferably a compound selected from the group consisting of an oxime compound, an α -hydroxy ketone compound, an α -amino ketone compound, and an acylphosphine compound, and even more preferably an oxime compound. Examples of the photopolymerization initiator include compounds described in paragraphs 0065 to 0111 of Japanese patent application laid-open No. 2014-130173 and Japanese patent application laid-open No. 6301489, the contents of which are incorporated herein.

Commercially available products of α -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (described above, manufactured by IGM Resins b.v.), Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (described above, manufactured by BASF). Commercially available α -aminoketone compounds include Omnirad 907, Omnirad 369E, Omnirad 379EG (produced by IGM Resins b.v., inc.), Irgacure 907, Irgacure 369E, Irgacure 379EG (produced by BASF, inc.). Commercially available products of acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V., Inc., mentioned above), Irgacure 819, and Irgacure TPO (manufactured by BASF, Inc., mentioned above).

Examples of oxime compounds include a compound described in Japanese patent laid-open No. 2001-233842, a compound described in Japanese patent laid-open No. 2000-080068, a compound described in Japanese patent laid-open No. 2006-342166, a compound described in J.C.S.Perkin II (1979, pp.1653-1660), a compound described in J.C.S.Perkin II (1979, pp.156-162), a compound described in Journal of Photopharmaceuticals Science and Technology (1995, pp.202-232), a compound described in Japanese patent laid-open No. 2000-066385, a compound described in Japanese patent laid-open No. 2000-080068, a compound described in Japanese patent laid-open No. 2004-534797, a compound described in Japanese patent laid-open No. 2006-2166, a compound described in Japanese patent laid-open No. 2017-019766, and a compound described in Japanese patent laid-open No. 35 6065596, Examples of the compound include a compound described in International publication No. 2015/152153, a compound described in International publication No. 2017/051680, a compound described in Japanese patent laid-open publication No. 2017-198865, a compound described in paragraphs 0025 to 0038 of International publication No. 2017/164127, and a compound described in International publication No. 2013/167515. Specific examples of the oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (BASF Corporation, supra), TR-PBG-304(Changzhou Tronly New Electronic Materials Co., Ltd.), and ADEKA OPTOMER N-1919 (photopolymerization initiator 2 described in ADEKA Corporation, Japanese patent laid-open publication No. 2012-014052). Further, as the oxime compound, a compound having no coloring property or a compound having high transparency and being less likely to be discolored is also preferably used. Examples of commercially available products include ADEKA ARKLS NCI-730, NCI-831 and NCI-930 (manufactured by ADEKA CORPORATION).

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include compounds described in Japanese patent application laid-open No. 2014-137466.

As the photopolymerization initiator, an oxime compound having a skeleton in which at least 1 benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of these oxime compounds include those described in international publication No. 2013/083505.

As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include compounds described in Japanese patent application laid-open No. 2010-262028, compounds 24, 36 to 40 described in Japanese patent application laid-open No. 2014-500852, and a compound (C-3) described in Japanese patent application laid-open No. 2013-164471.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably a dimer. Specific examples of oxime compounds having a nitro group include those described in paragraphs 0031 to 0047 of Japanese patent application laid-open No. 2013-114249, those described in paragraphs 0008 to 0012 and 0070 to 0079 of Japanese patent application laid-open No. 2014-137466, those described in paragraphs 0007 to 0025 of Japanese patent application laid-open No. 4223071, and those described in paragraphs ADEKA ARKLS NCI to 831 (manufactured by ADEKA CORPORATION).

As the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples thereof include OE-01 to OE-75 described in International publication No. 2015/036910.

Specific examples of oxime compounds preferably used in the present invention will be shown below, but the present invention is not limited to these.

[ chemical formula 14]

[ chemical formula 15]

The oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500nm, and more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm. From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365nm or 405nm is preferably high, more preferably 1000 to 300000, still more preferably 2000 to 300000, and particularly preferably 5000 to 200000. The molar absorption coefficient of a compound can be measured using a known method. For example, it is preferable to perform measurement using a spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian corporation) at a concentration of 0.01g/L using ethyl acetate.

As the photopolymerization initiator, a 2-functional or 3-or more-functional photoradical polymerization initiator may be used. By using such a photo radical polymerization initiator, two or more radicals are generated from one molecule of the photo radical polymerization initiator, and thus good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is reduced, the solubility in a solvent or the like is improved, and the deposition with time is less likely to occur, whereby the stability with time of the colored composition can be improved. Specific examples of the 2-functional or 3-functional or higher photo radical polymerization initiator include dimers of oxime compounds described in Japanese patent application No. 2010-527339, Japanese patent application No. 2011-524436, International publication No. 2015/004565, paragraphs 0407 to 0412 in Japanese patent application No. 2016-532675, paragraphs 0039 to 0055 in International publication No. 2017/033680, compounds (E) and compounds (G) described in Japanese patent application No. 2013-522445, examples of the photoinitiator include Cmpd1 to 7 described in International publication No. 2016/034963, oxime ester photoinitiators described in paragraphs 0007 of JP 2017-523465, photoinitiators described in paragraphs 0020 to 0033 of JP 2017-167399, photopolymerization initiators (A) described in paragraphs 0017 to 0026 of JP 2017-151342, and oxime compounds described in paragraphs 6469669.

The content of the photopolymerization initiator in the total solid content of the photosensitive resin composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less. The photopolymerization initiator may be used alone in 1 kind, or may be used in combination of 2 or more kinds. When 2 or more kinds are used in combination, the total amount of them is preferably within the above range.

Ultraviolet absorbent

The photosensitive resin composition of the present invention contains an ultraviolet absorber. The ultraviolet absorber is preferably a compound having a maximum absorption wavelength in a wavelength range of 300 to 380nm, and more preferably a compound having a maximum absorption wavelength in a wavelength range of 320 to 380 nm. Further, the ultraviolet absorber preferably has a molar absorption coefficient at a wavelength of 365nm of 5000L/mol^-1·cm^-1More preferably 10000 L.mol or more^-1·cm^-1Above, 30000 L.mol is more preferable^-1·cm^-1The above. The upper limit is preferably 100000 L.mol^-1·cm^-1The following.

Examples of the ultraviolet absorber include a conjugated diene compound, a methylbenzoyl compound, a triazine compound, a benzotriazole compound, a benzophenone compound, a salicylate compound, a coumarin compound, an acrylonitrile compound, a benzodithiazole compound, a cinnamic acid compound, an α - β unsaturated ketone, a quinolone compound, and the like, and from the viewpoint of easily obtaining more excellent light resistance, a conjugated diene compound, a benzotriazole compound, and a triazine compound are preferable.

The conjugated diene compound is preferably a compound represented by the following formula (UV-1).

[ chemical formula 16]

In the formula (UV-1), R¹And R²Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R¹And R²May be the same as or different from each other. Wherein R is¹And R²At least one of the above groups is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. R¹And R²Can be reacted with R¹And R²The bonded nitrogen atoms together form a cyclic amino group. Examples of the cyclic amino group include a piperidyl group, a morpholinyl group, a pyrrolidinyl group, a hexahydroaza (azepino) group, and a piperazinyl group. R¹And R²Each independently represents preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 5 carbon atoms.

In the formula (UV-1), R³And R⁴Each independently represents an electron withdrawing group. R³And R⁴Preferably each independently is acyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, nitro, alkylsulfonyl, arylsulfonyl, sulfonyloxy, or sulfamoyl, more preferably acyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, alkylsulfonyl, arylsulfonyl, sulfonyloxy, or sulfamoyl. And, R³And R⁴May be bonded to each other to form a cyclic electron withdrawing group. As R³And R⁴Examples of the cyclic electron-withdrawing group bonded to each other include a 6-membered ring containing two carbonyl groups.

From R of formula (UV-1)¹、R²、R³And R⁴At least 1 of which via the linking group may be in the form of a polymer derived from a monomer bonded to the vinyl group. Copolymers with other monomers are also possible.

The substituent of the ultraviolet absorber represented by the formula (UV-1) can be described in paragraphs 0024 to 0033 of Japanese patent laid-open No. 2009-265642, which is incorporated herein by reference. Specific examples of the ultraviolet absorber represented by the formula (UV-1) include compounds having the following structures and compounds described in paragraphs 0034 to 0036 of Japanese patent laid-open No. 2009-265642. Further, examples of commercially available ultraviolet absorbers represented by the formula (UV-1) include UV-503 (manufactured by DAITO CHEMICAL CO., LTD.).

[ chemical formula 17]

The methylbenzoyl compound is preferably a compound represented by the following formula (UV-2).

[ chemical formula 18]

In the formula (UV-2), R¹⁰¹And R¹⁰²Each independently represents a substituent, and m1 and m2 each independently represent an integer of 0 to 4.

As R¹⁰¹And R¹⁰²Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group and-NR^U1R^U2、-COR^U3、-COOR^U4、-OCOR^U5、-NHCOR^U6、-CONR^U7R^U8、-NHCONR^U9R^U10、-NHCOOR^U11、-SO₂R^U12、-SO₂OR^U13、-NHSO₂R^U14and-SO₂NR^U15R^U16。R^U1～R^U16Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group.

R¹⁰¹And R¹⁰The substituents represented by 2 are preferably each independently an alkyl group or an alkoxy group. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10. Examples of the alkyl group include linear, branched and cyclic, and preferably linear or branched, and more preferably branched. The number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 10. The alkoxy group is preferably straight-chain or branched, and more preferably branched.

In the formula (UV-2), R is preferred¹⁰¹And R¹⁰²One is an alkyl group and the other is a combination of alkoxy groups.

m1 and m2 each independently represent 0 to 4. m1 and m2 are each independently preferably 0 to 2, more preferably 0 to 1, and particularly preferably 1.

Specific examples of the compound represented by the formula (UV-2) include AVOBENZONE (AVOBENZONE) and the like.

The triazine compound is preferably a compound represented by the following formula (UV-3-1), (UV-3-2) or (UV-3-3).

[ chemical formula 19]

In the formula, R^d1Independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms or an arylalkyl group having 7 to 18 carbon atoms. The alkyl group, the alkenyl group, the aryl group, the alkylaryl group, and the arylalkyl group may have a substituent. Examples of the substituent include the groups described above for the substituent Ti.

In the formula, R^d2～R^d9Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms. The alkyl group, the alkenyl group, the aryl group, the alkylaryl group, and the arylalkyl group may have a substituent.Examples of the substituent include the groups described above for the substituent Ti.

Specific examples of the triazine compound include mono (hydroxyphenyl) triazine compounds such as 2- [4- [ (2-hydroxy-3-dodecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [4- [ (2-hydroxy-3-tridecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine and 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine; bis (hydroxyphenyl) triazine compounds such as 2, 4-bis (2-hydroxy-4-propoxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine, 2, 4-bis (2-hydroxy-3-methyl-4-propoxyphenyl) -6- (4-methylphenyl) -1,3, 5-triazine, 2, 4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine and the like; tris (hydroxyphenyl) triazine compounds such as 2, 4-bis (2-hydroxy-4-butoxyphenyl) -6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-4-octyloxyphenyl) -1,3, 5-triazine, 2,4, 6-tris [ 2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl ] -1,3, 5-triazine, and the like. Examples of commercially available triazine compounds include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479 (described above, manufactured by BASF corporation).

The benzotriazole compound is preferably a compound represented by the following formula (UV-4).

[ chemical formula 20]

In the formula, R^e1～R^e3Independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms or an arylalkyl group having 7 to 18 carbon atoms. The alkyl group, the alkylaryl group and the arylalkyl group may have a substituent. Examples of the substituent include those described for the substituent Ti above, and an alkoxycarbonyl group having 1 to 9 carbon atoms is preferable.

Specific examples of the benzotriazole compound include 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-3 ' -tert-amyl-5 ' -isobutylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-3 ' -isobutyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-3 ' -isobutyl-5 ' -propylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3', 5 '-di-tert-butylphenyl) benzotriazole, 2- (2' -hydroxy-5 '-methylphenyl) benzotriazole, 2- [ 2' -hydroxy-5 '- (1,1,3, 3-tetramethyl) phenyl ] benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxy, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-hydroxy-5-methylphenyl) benzotriazole, 2- [2- (2-hydroxy-5' - (1,1, 3-tetramethyl) phenyl ] benzotriazole -methyl-1-phenylethyl) -4- (1,1,3, 3-tetramethylbutyl) phenol and the like. Examples of commercially available products include TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 326, TINUVIN 328, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 171, and TINUVIN 1130 (manufactured by BASF Co., Ltd.). As the benzotriazole compound, the MYUA series manufactured by MIYOSHI OIL & FAT co.

Examples of the benzophenone compound include 2,2' -dihydroxy-4-methoxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2', 4,4' -tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-octyloxybenzophenone and the like. Commercially available benzophenone compounds include UVINUL a, UVINUL 3049, and UVINUL 3050 (manufactured by BASF corporation, above).

Examples of the salicylate compound include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

Examples of the coumarin compound include coumarin-4, 4-hydroxycoumarin, and 7-hydroxycoumarin.

Examples of the acrylonitrile compound include ethyl 2-cyano-3, 3-diphenylacrylate and 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate.

The content of the ultraviolet absorber in the total solid content of the photosensitive resin composition is 0.1-10% by mass. The upper limit is preferably 9.5% by mass or less, and more preferably 9% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. If the content of the ultraviolet absorber is 0.1% by mass or more, the light resistance of the obtained cured film can be improved. When the content of the ultraviolet absorber is 10% by mass or less, a cured film in which occurrence of color mixing with pixels of other hues is suppressed can be formed. In addition, when the photosensitive resin composition is used to form pixels by photolithography, the resolution of the photosensitive resin composition can be improved, and pixels with good rectangularity can be formed.

The photosensitive resin composition of the present invention preferably contains 1 to 200 parts by mass of an ultraviolet absorber per 100 parts by mass of a photopolymerization initiator. According to this aspect, both the resolution and the light resistance can be achieved at a higher level. The upper limit of the content of the ultraviolet absorber is preferably 190 parts by mass or less, and more preferably 170 parts by mass or less. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more.

The photosensitive resin composition of the present invention preferably contains 0.1 to 100 parts by mass of an ultraviolet absorber per 100 parts by mass of the polymerizable compound. According to this aspect, both the resolution and the light resistance can be achieved at a higher level. The upper limit of the content of the ultraviolet absorber is preferably 80 parts by mass or less, and more preferably 50 parts by mass or less. The lower limit is preferably 1 part by mass or more, and more preferably 5 parts by mass or more.

The number of the ultraviolet absorbers contained in the photosensitive resin composition of the present invention may be only 1, or may be 2 or more. When the photosensitive resin composition of the present invention contains 2 or more ultraviolet absorbers, the total amount of these is within the above range.

Solvent

The photosensitive resin composition of the present invention contains a solvent. The solvent is not limited as long as it satisfies the solubility of each component and the coatability of the photosensitive resin composition. Examples of the solvent include organic solvents. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For details, reference can be made to paragraph 0223 of international publication No. 2015/166779, which is incorporated into this specification. Also, ester solvents in which a cyclic alkyl group is substituted and ketone solvents in which a cyclic alkyl group is substituted can be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, methylene chloride, methyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, 3-methoxy-N, N '-dimethylpropionamide, and 3-butoxy-N, N' -dimethylpropionamide. Among them, from the viewpoint of environmental factors and the like, there are cases where it is preferable to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, and the like) as an organic solvent (for example, 50 mass ppm (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less may be set with respect to the total amount of the organic solvent).

In the present invention, it is preferable to use an organic solvent having a small metal content, and the metal content of the organic solvent is preferably, for example, 10 parts per billion (ppb) or less by mass. Organic solvents of the quality ppt (parts per million) grade, as provided, for example, by Toyo Gosei co., ltd. (daily journal of chemical industry, 11/13/2015), may be used as required.

Examples of the method for removing impurities such as metals from an organic solvent include distillation (molecular distillation, membrane distillation, or the like) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The organic solvent may contain isomers (compounds having the same atomic number but different structures). The isomer may include only one kind or a plurality of kinds.

The content of the peroxide in the organic solvent is preferably 0.8mmol/L or less, and more preferably substantially no peroxide.

The content of the solvent in the photosensitive resin composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and still more preferably 30 to 90% by mass.

In view of environmental control, the photosensitive resin composition of the present invention preferably contains substantially no environmental control substance. In the present invention, the substantial absence of the environmental control substance means that the content of the environmental control substance in the photosensitive resin composition is 50 mass ppm or less, preferably 30 mass ppm or less, more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Examples of the environment-controlling substance include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, and the like. These are registered as environmental control substances according to the rules of reach (registration Evaluation Authorization and recovery of chemicals), the prtr (polar Release and Transfer register) method, voc (volatile Organic compounds) control, and the like, and the amount of use and the operation method are strictly controlled. In the production of each component used in the photosensitive resin composition, these compounds are sometimes used as a solvent and sometimes mixed into the photosensitive resin composition as a residual solvent. From the viewpoint of safety to humans and environmental concerns, these substances are preferably reduced as much as possible.

As a method for reducing the environmental controlled substance, there is a method in which the internal pressure of the system is reduced by heating or reducing the internal pressure to a boiling point of the environmental controlled substance or higher, and the environmental controlled substance is distilled from the internal pressure of the system to be reduced. In addition, when a small amount of the environmental control substance is distilled, it is effective to azeotropically dissolve the solvent having the same boiling point as the above solvent in order to improve efficiency. When the compound having radical polymerizability is contained, the distillation under reduced pressure may be performed by adding a polymerization inhibitor or the like in order to suppress the crosslinking between molecules by the radical polymerization reaction in the distillation under reduced pressure. These distillation removal methods can be performed in any of a raw material stage, a stage of a product of reacting raw materials (for example, a resin solution after polymerization and a polyfunctional monomer solution), a stage of a photosensitive resin composition produced by mixing these compounds, and the like.

Pigment derivatives

The photosensitive resin composition of the present invention may contain a pigment derivative. The pigment derivative is used as a dispersing aid for the pigment. Examples of the pigment derivative include compounds having a structure in which a part of a chromophore is substituted with an acid group or a base group.

Examples of the color developing group constituting the pigment derivative include a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a phthalocyanine skeleton, an anthraquinone skeleton, a quinacridone skeleton, a dioxazine skeleton, a perinone skeleton, a perylene skeleton, a thioindigo skeleton, an isoindoline skeleton, an isoindolinone skeleton, a quinophthalone skeleton, a reducing skeleton, a metal complex skeleton, and the like, and the quinoline skeleton, the benzimidazolone skeleton, the diketopyrrolopyrrole skeleton, the azo skeleton, the quinophthalone skeleton, the isoindoline skeleton, and the phthalocyanine skeleton are preferable, and the azo skeleton and the benzimidazolone skeleton are more preferable.

Examples of the acid group of the pigment derivative include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and salts thereof. Examples of the atom or atomic group constituting the salt include alkali metal ions (Li)⁺、Na⁺、K⁺Etc.), alkaline earth metal ions (Ca)²⁺、Mg²⁺Etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ions, etc.

Examples of the base group of the pigment derivative include an amino group, a pyridyl group, a salt thereof, a salt of an ammonium group, and a phthalimidomethyl group. Examples of the amino group include-NH₂Dialkylamino, alkylarylamino, diarylamino, cyclic amino, and the like. Examples of the atom or atomic group constituting the salt include a hydroxide ion, a halogen ion, a carboxylate ion, a sulfonate ion, a phenoxy ion, and the like.

As the pigment derivative, a pigment derivative having excellent visible transparency (hereinafter, also referred to as a transparent pigment derivative) can be used. The maximum value (. epsilon.max) of the molar absorptivity of the transparent pigment derivative in the wavelength range of 400 to 700nm is preferably 3000L. mol^-1·cm^-1Hereinafter, more preferably 1000 L.mol^-1·cm^-1Hereinafter, more preferably 100 L.mol^-1·cm^-1The following. The lower limit of ε max is, for example, 1L. mol^-1·cm^-1Above, it may be 10 L.mol^-1·cm^-1The above.

Specific examples of the pigment derivative include Japanese patent application laid-open Nos. 56-118462, 63-264674, 01-217077, 03-009961, 03-026767, 03-153780, 03-045662, 04-285669, 06-145546, 06-212088, 06-240158, 10-030063, 10-195326, 0086-0098 of International publication No. 2011/024896, 0063-0094 of International publication No. 2012/102399, 0082 of International publication No. 2017/038252, and 0171 of 2015-151530, The compounds described in paragraphs 0162 to 0183 of Japanese patent laid-open publication No. 2011-252065, Japanese patent laid-open publication No. 2003-081972, Japanese patent laid-open publication No. 5299151, Japanese patent laid-open publication No. 2015-172732, Japanese patent laid-open publication No. 2014-199308, Japanese patent laid-open publication No. 2014-085562, Japanese patent laid-open publication No. 2014-035351, and Japanese patent laid-open publication No. 2008-565 081081.

The content of the pigment derivative is preferably 1 to 30 parts by mass per 100 parts by mass of the pigment. The lower limit is preferably 2 parts by mass or more, and more preferably 3 parts by mass or more. The upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less. The pigment derivative may be used alone in 1 kind, or may be used in combination of 2 or more kinds. When 2 or more kinds are used in combination, the total amount is preferably within the above range.

< Compound having epoxy group >

The photosensitive resin composition of the present invention may contain a compound having an epoxy group (hereinafter, also referred to as an epoxy compound). Examples of the epoxy compound include compounds having 1 or more epoxy groups in 1 molecule, and preferably compounds having two or more epoxy groups. The epoxy compound preferably has 1 to 100 epoxy groups in 1 molecule. The upper limit of the number of epoxy groups can be set to, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups is preferably two or more. As the epoxy compound, compounds described in paragraphs 0034 to 0036 of Japanese patent application laid-open No. 2013-011869, paragraphs 0147 to 0156 of Japanese patent application laid-open No. 2014-043556, paragraphs 0085 to 0092 of Japanese patent application laid-open No. 2014-089408, and compounds described in Japanese patent application laid-open No. 2017-179172 can be used. These are incorporated into the present specification.

The epoxy compound may be a low molecular compound (for example, a molecular weight of less than 2000, and further a molecular weight of less than 1000), or a high molecular compound (macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). The weight average molecular weight of the epoxy compound is preferably 200 to 100000, more preferably 500 to 50000. The upper limit of the weight average molecular weight is preferably 10000 or less, more preferably 5000 or less, and further preferably 3000 or less.

Examples of commercially available epoxy compounds include EHPE3150 (manufactured by Daicel Corporation) and EPICLON-695 (manufactured by DIC Corporation).

The content of the epoxy compound in the total solid content of the photosensitive resin composition is preferably 0.1 to 20 mass%. The lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, preferably 15% by mass or less, and more preferably 10% by mass or less. The epoxy compound contained in the photosensitive resin composition may be only 1 kind, or may be 2 or more kinds. When the number of the (2) or more is more than 2, the total amount is preferably within the above range.

< Compounds containing furyl group >)

The photosensitive resin composition of the present invention preferably contains a compound containing a furyl group (hereinafter, also referred to as a furyl group-containing compound). According to this embodiment, a photosensitive resin composition having excellent curability at low temperature can be provided.

The structure of the furyl group-containing compound is not particularly limited as long as it contains a furyl group (a group obtained by removing 1 hydrogen atom from furan). As the furyl group-containing compound, the compounds described in paragraphs 0049 to 0089 of Japanese patent laid-open publication No. 2017-194662 can be used. Further, compounds described in Japanese patent laid-open Nos. 2000-233581, 1994-271558, 1994-293830, 1996-239421, 1998-508655, 2000-001529, 2003-183348, 2006-193628, 2007-186684, 2010-265377, 2011-170170069, and the like can be used.

The furyl group-containing compound may be a monomer or a polymer. The polymer is preferable for the reason of improving the durability of the obtained cured film. In the case of a polymer, the weight average molecular weight is preferably 2000 to 70000. The upper limit is preferably 60000 or less, more preferably 50000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and further preferably 5000 or more. The polymer type furyl group-containing compound is a component corresponding to the resin in the photosensitive resin composition of the present invention.

As the monomer type furyl group-containing compound (hereinafter also referred to as furyl group-containing monomer), there can be mentioned a compound represented by the following formula (fur-1).

[ chemical formula 21]

In the formula, Rf¹Represents a hydrogen atom or a methyl group, Rf²Represents a 2-valent linking group.

As Rf²The 2-valent linking group may be an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, or a combination of 2 or more thereof. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The alkylene group may be any of linear, branched, and cyclic. The number of carbon atoms of the arylene group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. Alkylene radicalAnd the arylene group may have a substituent. Examples of the substituent include a hydroxyl group and the like.

The furyl group-containing monomer is preferably a compound represented by the following formula (fur-1-1).

[ chemical formula 22]

In the formula, Rf¹Represents a hydrogen atom or a methyl group, Rf¹¹represents-O-or-NH-, Rf¹²Represents a single bond or a 2-valent linking group. As Rf¹²The 2-valent linking group may be an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, or a combination of 2 or more thereof. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The alkylene group may be any of linear, branched, and cyclic. The number of carbon atoms of the arylene group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxyl group and the like.

Specific examples of the furyl group-containing monomer include compounds having the following structures. In the following structural formula, Rf¹Represents a hydrogen atom or a methyl group.

[ chemical formula 23]

The polymer-type furyl group-containing compound (hereinafter also referred to as furyl group-containing polymer) is preferably a resin containing a furyl group-containing repeating unit, and more preferably a resin containing a repeating unit derived from a compound represented by the above formula (fur-1). The concentration of the furyl group in the furyl group-containing polymer is preferably 0.5 to 6.0mmol, more preferably 1.0 to 4.0mmol, per 1g of the furyl group-containing polymer. When the concentration of the furyl group is 0.5mmol or more, preferably 1.0mmol or more, a pixel having excellent solvent resistance and the like can be easily formed. When the concentration of the furyl group is 6.0mmol or less, preferably 4.0mmol or less, the stability of the photosensitive resin composition with time becomes good.

The polymer containing a furyl group may contain, in addition to the repeating unit having a furyl group, a repeating unit having an acid group and/or a repeating unit having a polymerizable group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Examples of the polymerizable group include ethylenically unsaturated bond-containing groups such as a vinyl group, (meth) allyl group, and (meth) acryloyl group. When the polymer having a furyl group contains a repeating unit having an acid group, the acid value is preferably 10 to 200mgKOH/g, more preferably 40 to 130 mgKOH/g.

When the furyl group-containing polymer contains a repeating unit having a polymerizable group, a pixel having excellent solvent resistance and the like can be more easily formed.

The furyl group-containing polymer can be produced by the method described in paragraphs 0052 to 0101 of Japanese patent application laid-open No. 2017-194662.

The content of the compound containing a furyl group in the total solid content of the photosensitive resin composition is preferably 0.1 to 70 mass%. The lower limit is preferably 2.5% by mass or more, more preferably 5.0% by mass or more, and further preferably 7.5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less. When a furyl group-containing polymer is used as the furyl group-containing compound, the content of the furyl group-containing polymer in the resin contained in the photosensitive resin composition is preferably 0.1 to 100% by mass. The lower limit is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more. The upper limit is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 70 parts by mass or less. The number of the furyl group-containing compounds may be only 1, or may be 2 or more. In the case of 2 or more species, the total amount is preferably within the above range.

Silane coupling agent

The photosensitive resin composition of the present invention may contain a silane coupling agent. In the present invention, the silane coupling agent refers to a silane compound having a hydrolyzable group and a functional group other than the hydrolyzable group. The hydrolyzable group is a substituent which is directly bonded to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, with an alkoxy group being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a thioether group, an isocyanate group, and a phenyl group, and an amino group, a (meth) acryloyl group, and an epoxy group are preferable. Specific examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of Japanese patent application laid-open No. 2009-288703 and compounds described in paragraphs 0056 to 0066 of Japanese patent application laid-open No. 2009-242604, and these contents are incorporated herein.

The content of the silane coupling agent in the total solid content of the photosensitive resin composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The number of silane coupling agents may be only 1, or may be 2 or more. In the case of 2 or more species, the total amount is preferably within the above range.

(curing accelerator)

The photosensitive resin composition of the present invention may contain a curing accelerator. Examples of the curing accelerator include a polyfunctional thiol compound having two or more mercapto groups in the molecule. The polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like. The polyfunctional thiol compound is preferably a secondary alkanethiol, and more preferably a compound represented by the formula (T1).

Formula (T1)

[ chemical formula 24]

(in the formula (T1), n represents an integer of 2-4, and L represents a 2-4 valent linking group.)

In the formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, and n is particularly preferably 2, and L is an alkylene group having 2 to 12 carbon atoms.

Furthermore, methylol compounds (for example, compounds exemplified as the crosslinking agent in 0246 of Japanese patent laid-open publication No. 2015-034963), amines, phosphonium salts, amidine salts, and amide compounds (the curing agent described in 0186 of Japanese patent laid-open publication No. 2013-041165) can be used as the curing accelerator, examples of the base generating agent include an alkali generating agent (e.g., an ionic compound described in Japanese patent application laid-open No. 2014-055114), a cyanate ester compound (e.g., a compound described in paragraph 0071 of Japanese patent application laid-open No. 2012-150180), an alkoxysilane compound (e.g., an alkoxysilane compound having an epoxy group described in Japanese patent application laid-open No. 2011-253054), an onium salt compound (e.g., a compound exemplified as an acid generating agent in paragraph 0216 of Japanese patent application laid-open No. 2015-034963, and a compound described in Japanese patent application laid-open No. 2009-941809).

The content of the curing accelerator in the total solid content of the photosensitive resin composition is preferably 0.3 to 8.9% by mass, and more preferably 0.8 to 6.4% by mass.

Polymerization inhibitor

The photosensitive resin composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxylamine salts (ammonium salts, cerium oxide salts, and the like). Among them, p-methoxyphenol is preferable. The content of the polymerization inhibitor in the total solid content of the photosensitive resin composition is preferably 0.0001 to 5% by mass.

Surface active agent

The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. The surfactant includes surfactants described in paragraphs 0238 to 0245 of International publication No. 2015/166779, which is incorporated herein by reference.

In the present invention, the surfactant is preferably a fluorine-based surfactant. By containing the fluorine-based surfactant in the photosensitive resin composition, the liquid characteristics (particularly, fluidity) can be further improved, and the liquid saving property can be further improved. Further, a cured film having a small thickness unevenness can be formed.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-based surfactant having a fluorine content within this range is effective from the viewpoint of uniformity of the thickness of the coating film and liquid saving, and has good solubility in the photosensitive resin composition.

Examples of the fluorine-based surfactant include surfactants described in paragraphs 0060 to 0064 of Japanese patent application laid-open No. 2014-041318 (corresponding paragraphs 0060 to 0064 of International publication No. 2014/017669), and surfactants described in paragraphs 0117 to 0132 of Japanese patent application laid-open No. 2011-132503, and these are incorporated herein. Commercially available fluorine-based surfactants include MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS-330 (manufactured by DIC Corporation, supra), FLUORAD FC430, FC431, FC171 (manufactured by Sumitomo 3MLimited, supra), SURFON S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC INC., supra), PolyFox 636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc., supra), and the like.

Further, as the fluorine-based surfactant, a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound is also preferably used. Examples of such fluorine-containing surfactants include those described in Japanese patent application laid-open No. 2016-216602, the contents of which are incorporated herein.

The fluorine-based surfactant may be a block polymer. The fluorine-containing surfactant can also preferably use a fluorine-containing polymer compound containing: a repeating unit derived from a (meth) acrylate compound having a fluorine atom; and a repeating unit derived from a (meth) acrylate compound having two or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups). Further, examples of the fluorinated surfactant used in the present invention include the fluorinated surfactants described in paragraphs 0016 to 0037 of Japanese patent application laid-open No. 2010-032698, and the following compounds.

[ chemical formula 25]

The weight average molecular weight of the compound is preferably 3000 to 50000, for example 14000. In the above compounds,% representing the proportion of the repeating unit is mol%.

Further, as the fluorine-containing surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in a side chain can be used. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese patent application laid-open No. 2010-164965, MEGAFACE RS-101, RS-102, and RS-718K, RS-72-K manufactured by DIC Corporation, and the like. Further, as the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of Japanese patent application laid-open No. 2015-117327 can be used.

Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (available from BASF Corporation), Tetronic 304, 701, 704, 901, 904, 150R1 (available from BASF Corporation), Solsperse 20000 (available from Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (available from Fufillm Wako Pure Corporation), PIOND-6112, D-6112-W, D-6315(Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440(Nissin Chemical Co., Ltd.), and the like.

Examples of the silicon-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Chemical Co., LTD., Ltd.), BYK307, BYK323, BYK330 (manufactured by BYK-Chemie, etc.).

The content of the surfactant in the total solid content of the photosensitive resin composition is preferably 0.001 to 5.0% by mass, and more preferably 0.005 to 3.0% by mass. The number of the surfactants may be only 1, or may be 2 or more. In the case of 2 or more species, the total amount is preferably within the above range.

[ antioxidant ]

The photosensitive resin composition of the present invention may contain an antioxidant. Examples of the antioxidant include phenol compounds, phosphite compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. As a preferred phenol compound, a hindered phenol compound is exemplified. The compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group is preferable. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. Further, the antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. Further, as the antioxidant, a phosphorus-based antioxidant can be preferably used.

The content of the antioxidant in the total solid content of the photosensitive resin composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. The antioxidant may be used in 1 type or 2 or more types. When 2 or more are used, the preferable total amount is within the above range.

Other components

The photosensitive resin composition of the present invention may contain, if necessary, a sensitizer, a filler, a thermosetting accelerator, a plasticizer, and other auxiliary agents (for example, conductive particles, a filler, an antifoaming agent, a flame retardant, a leveling agent, a peeling accelerator, a fragrance, a surface tension adjusting agent, a chain transfer agent, and the like). By appropriately containing these components, properties such as physical properties of the film can be adjusted. For example, the components can be described in paragraphs 0183 of Japanese patent application laid-open No. 2012 and 003225 (0237 of the corresponding US patent application laid-open No. 2013/0034812), paragraphs 0101 to 0104 and paragraphs 0107 to 0109 of Japanese patent application laid-open No. 2008 and 250074, and the contents of these can be incorporated in the present specification. The photosensitive resin composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant includes a compound in which a site functioning as an antioxidant is protected with a protecting group, and the compound is heated at 100 to 250 ℃ or at 80 to 200 ℃ in the presence of an acid/base catalyst, whereby the protecting group is released to function as an antioxidant. Examples of the potential antioxidant include compounds described in International publication Nos. 2014/021023, 2017/030005 and JP-A-2017-008219. Examples of commercially available potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA Corporation). Further, as described in japanese patent application laid-open No. 2018-155881, c.i. pigment yellow 129 can be added for the purpose of improving weather resistance.

The photosensitive resin composition of the present invention may contain a metal oxide in order to adjust the refractive index of the obtained cured film. Examples of the metal oxide include TiO₂、ZrO₂、Al₂O₃、SiO₂And the like. The primary particle diameter of the metal oxide is preferably 1 to 100nm, more preferably 3 to 70nm, and further preferably 5 to 50 nm. The metal oxide may have a core-shell structure. And, in this case, the nucleusThe portion may be hollow.

The photosensitive resin composition of the present invention may contain a light resistance improver. Examples of the light resistance improver include compounds described in paragraphs 0036 to 0037 of Japanese patent application laid-open No. 2017-198787, compounds described in paragraphs 0029 to 0034 of Japanese patent application laid-open No. 2017-146350, compounds described in paragraphs 0036 to 0037 and paragraphs 0049 to 0052 of Japanese patent application laid-open No. 2017-129774, compounds described in paragraphs 0031 to 0034 and 0058 to 0059 of Japanese patent application laid-open No. 2017-122803, compounds described in paragraphs 20156 to 0037 and paragraphs 0051 to 0054 of Japanese patent application laid-open No. 0025 to 0039 of International publication No. 2017/164127, compounds described in paragraphs 0034 to 0047 of Japanese patent application laid-open No. 2017-004546, compounds described in paragraphs 0129 to 0041 of Japanese patent application laid-open No. 2012-025116, and compounds described in paragraphs 0125 to 004604 of Japanese patent application laid-open No. 0101-0045, The compounds described in paragraphs 0018 to 0021 in Japanese patent laid-open No. 2012 and 103475, the compounds described in paragraphs 0015 to 0018 in Japanese patent laid-open No. 2011 and 257591, the compounds described in paragraphs 0017 to 0021 in Japanese patent laid-open No. 2011 and 191483, the compounds described in paragraphs 0108 to 0116 in Japanese patent laid-open No. 2011 and 145668, the compounds described in paragraphs 0103 to 0153 in Japanese patent laid-open No. 2011 and 253174, and the like.

In the photosensitive resin composition of the present invention, the content of free metal not bonded or coordinated to a pigment or the like is preferably 100ppm or less, more preferably 50ppm or less, further preferably 10ppm or less, and particularly preferably substantially none. According to this embodiment, effects such as stabilization of pigment dispersibility (suppression of aggregation), improvement of spectroscopic characteristics accompanying improvement of dispersibility, stabilization of curable components, suppression of elution conductivity fluctuation accompanying metal atoms and metal ions, and improvement of display characteristics can be expected. Further, the effects described in Japanese patent laid-open Nos. 2012-153796, 2000-345085, 2005-200560, 08-043620, 2004-145078, 2014-119487, 2010-083997, 2017-090930, 2018-025612, 2018-025797, 2017-155228, 2018-036521 and the like can be obtained. Examples of the kind of the free metal include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Ni, Cd, Pb, and Bi. In the photosensitive resin composition of the present invention, the content of free halogen not bonded or coordinated to a pigment or the like is preferably 100ppm or less, more preferably 50ppm or less, further preferably 10ppm or less, and particularly preferably substantially none. Examples of the halogen include F, Cl, Br, I and anions thereof. Examples of a method for reducing the amount of free metal or halogen in the photosensitive resin composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.

The photosensitive resin composition of the present invention is also preferably substantially free of terephthalate. The term "substantially free" means that the content of terephthalate in the total amount of the photosensitive resin composition is 1000 mass ppb or less, more preferably 100 mass ppb or less, and particularly preferably zero.

The water content of the photosensitive resin composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

The photosensitive resin composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film shape (flatness, etc.) and adjusting the film thickness. The viscosity can be appropriately selected as needed, but is preferably 0.3 to 50 mPas, more preferably 0.5 to 20 mPas at 25 ℃. As a method for measuring the viscosity, for example, a viscometer RE85L (rotor: 1 ℃ C. 34'. times.R 24, measurement range: 0.6 to 1200 mPas) manufactured by TOKI SANGYO CO., LTD. can be used, and the measurement can be carried out in a state where the temperature is adjusted to 25 ℃.

When the photosensitive resin composition of the present invention is used as a color filter for a liquid crystal display device, the voltage holding ratio of a liquid crystal display element having a color filter is preferably 70% or more, and more preferably 90% or more. The known methods for obtaining a high voltage holding ratio can be combined as appropriate, and typical methods include using a raw material having a high purity (for example, reducing ionic impurities) and controlling the amount of acidic functional groups in the composition. The voltage holding ratio can be measured by, for example, the methods described in sections 0243 of jp 2011-.

< storage Container >

The container for the photosensitive resin composition of the present invention is not particularly limited, and a known container can be used. Further, as the storage container, in order to suppress the mixing of impurities into the raw material or the photosensitive resin composition, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 kinds of 6-layer resins or a bottle in which 6 kinds of resins are formed into a 7-layer structure. Examples of such a container include those disclosed in Japanese patent laid-open publication No. 2015-123351. Further, for the purpose of preventing elution of metal from the inner wall of the container, improving storage stability of the photosensitive resin composition, suppressing deterioration of components, and the like, the inner wall of the container is preferably made of glass, stainless steel, or the like.

< preparation of photosensitive resin composition >

The photosensitive resin composition of the present invention can be prepared by mixing the above components. When the photosensitive resin composition is prepared, all the components may be dissolved and/or dispersed in a solvent at the same time to prepare the photosensitive resin composition, or when the components are used (applied), the components may be mixed as a solution or dispersion of two or more, as appropriate, to prepare the photosensitive resin composition.

In addition, the preparation of the photosensitive resin composition preferably includes a process of dispersing the pigment. In the process of dispersing the pigment, examples of mechanical forces used for dispersing the pigment include compression, pressing, impact, shearing, cavitation and the like. Specific examples of these processes include bead milling, sand milling, roll milling, ball milling, paint stirring, microfluid, high-speed impeller, sand mixing, jet mixing, high-pressure wet micronization, ultrasonic dispersion, and the like. In addition, in the pulverization of the pigment by sanding (bead milling), it is preferable to perform treatment under the condition that the pulverization efficiency is improved by using the microbeads having a small diameter and improving the filling rate of the microbeads or the like. Further, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. Further, as the process and the dispersing machine for dispersing the pigment, it is preferable to use a process and a dispersing machine described in "a dispersion technology university, johaokiko co., ltd. release, 7/15/2005" or "a dispersion technology centered around a suspension (solid/liquid dispersion system) and an industrial practical application comprehensive data set, published by the ministry of business and development, 10/1978", and paragraph 0022 of japanese patent application laid-open No. 2015-157893. In the process of dispersing the pigment, the particle size reduction treatment can be performed by the salt milling step. For example, the raw materials, facilities, and treatment conditions used in the salt milling step can be described in japanese patent application laid-open nos. 2015-194521 and 2012-046629.

In the production of the photosensitive resin composition, the photosensitive resin composition is preferably filtered through a filter for the purpose of removing foreign matters, reducing defects, and the like. The filter may be used without any particular limitation as long as it is conventionally used for filtration applications and the like. Examples of the filter include filters made of materials such as a fluororesin such as Polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (e.g., nylon-6, 6), and a polyolefin resin (including a high-density, ultrahigh-molecular-weight polyolefin resin) such as Polyethylene and Polypropylene (PP). Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.

The pore diameter of the filter is preferably 0.01 to 7.0. mu.m, more preferably 0.01 to 3.0. mu.m, and still more preferably 0.05 to 0.5. mu.m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. With regard to the pore size value of the filter, reference can be made to the nominal value of the filter manufacturer. The filters can be any of the filters provided by NIHON PALL LTD. (DFA4201NIEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (Formerly Nippon micro liquid Co., Ltd.), and KITZMICROSFILTER CORPORATION, etc.

Further, as the filter, a fibrous filter medium is also preferably used. Examples of the fibrous filter medium include polypropylene fibers, nylon fibers, and glass fibers. Commercially available products include ROKI TECHNO CO., SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by LTD.

When filters are used, different filters (e.g., a1 st filter and a 2 nd filter, etc.) may be combined. In this case, the filtration with each filter may be performed only 1 time, or may be performed 2 times or more. Also, filters of different pore sizes may be combined within the above range. Further, the following may be performed: in the case of filtration using the 1 st filter, only the dispersion liquid is filtered, and after mixing other components, filtration is performed using the 2 nd filter.

< cured film >

The cured film of the present invention is obtained from the photosensitive resin composition of the present invention. The cured film of the present invention can be preferably used as a colored pixel of a color filter. As the colored pixel, a cyan pixel is preferable. The thickness of the cured film of the present invention can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

The average transmittance of the cured film of the present invention in the thickness direction of the film of light having a wavelength in the range of 400 to 530nm is preferably 70% or more, more preferably 80% or more, and still more preferably 85% or more. The minimum value of the transmittance of light having a wavelength of 400 to 530nm in the thickness direction of the film is preferably 40% or more, more preferably 50% or more, and still more preferably 60% or more. The average transmittance of light having a wavelength of 610 to 700nm in the thickness direction of the film is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less. The maximum value of the transmittance of light having a wavelength of 610 to 700nm in the thickness direction of the film is preferably 40% or less, more preferably 30% or less, and still more preferably 25% or less.

In the transmission spectrum of the cured film of the present invention with respect to light having a wavelength in the range of 400 to 700nm in the thickness direction of the film, it is preferable that the peak of the transmittance is present in the range of 400 to 530 nm. It is preferable that the wavelength at which the transmittance reaches 50% of the peak value is present in the wavelength range of 540 to 600nm (hereinafter, this wavelength is also referred to as λ)^T50). Preferably, the wavelength of the light having a transmittance of 20% of the peak value is present in the wavelength range of 560 to 620nm (hereinafter, this wavelength is also referred to as λ)^T20)。λ^T50Preferably, the wavelength is in the range of 545 to 595nm, and more preferably in the range of 550 to 590 nm. Lambda [ alpha ]^T20Preferably in the wavelength range of 565 to 615nm, more preferably in the wavelength range of 560 to 610 nm. And, λ^T20 and lambda^T50Difference between (λ)^T20-λ^T50) Preferably 5 to 80nm, more preferably 7 to 50nm, and still more preferably 10 to 30 nm.

< color filter >

Next, the color filter of the present invention will be explained. The color filter of the present invention has the cured film of the present invention. More preferably, a pixel as a color filter has the cured film of the present invention. It is further preferable that the cyan pixel as a color filter has the cured film of the present invention. The color filter of the present invention can be used for a solid-state imaging device such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor), an image display device, or the like.

The thickness of the cured film of the present invention in the color filter of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

The width of the pixel of the color filter of the present invention is preferably 0.5 to 20.0 μm. The lower limit is preferably 1.0 μm or more, and more preferably 2.0 μm or more. The upper limit is preferably 15.0 μm or less, and more preferably 10.0 μm or less. The Young's modulus of the pixel is preferably 0.5 to 20GPa, and more preferably 2.5 to 15 GPa.

Each pixel included in the color filter of the present invention preferably has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100nm or lessMore preferably 40nm or less, and still more preferably 15nm or less. The lower limit is not particularly limited, but is preferably 0.1nm or more, for example. The surface roughness of the pixel can be measured using, for example, AFM (atomic force microscope) Dimension3100 manufactured by Veeco. The water contact angle on the pixel can be set to a preferable value as appropriate, and is usually within a range of 50 to 110 °. The contact angle can be measured, for example, using a contact angle meter CV-DT · a (manufactured by Kyowa Interface Science co., ltd.). Further, the volume resistance value of the pixel is preferably high. Specifically, the volume resistance value of the pixel is preferably 10⁹Omega cm or more, more preferably 10¹¹Omega cm or more. The upper limit is not particularly limited, and is preferably 10¹⁴Omega cm or less. The volume resistance value of the pixel can be measured using, for example, the ultra high resistance meter 5410 (manufactured by ADVANTEST CORPORATION).

In the color filter of the present invention, a protective layer may be provided on the surface of the cured film of the present invention. By providing the protective layer, various functions such as oxidation blocking, low reflection, hydrophilicity/hydrophobicity control, and shielding of light having a specific wavelength (ultraviolet rays, near infrared rays, and the like) can be provided. The thickness of the protective layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. Examples of the method for forming the protective layer include a method of coating a resin composition dissolved in an organic solvent, a chemical vapor deposition method, and a method of bonding a molded resin with a bonding material. Examples of the component constituting the protective layer include (meth) acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polystyrene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, polyurethane resin, aramid (aramid) resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine resin, polycarbonate resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al₂O₃、Mo、SiO₂、Si₂N₄Etc. may also contain 2 kindsThe above components. For example, in the case of a protective layer for the purpose of preventing oxidation, the protective layer preferably contains a polyol resin or SiO₂、Si₂N₄. In the case of a protective layer for the purpose of reducing reflection, the protective layer preferably contains a (meth) acrylic resin or a fluororesin.

When the protective layer is formed by applying the resin composition, a known method such as a spin coating method, a casting method, a screen printing method, an ink jet method, or the like can be used as a method for applying the resin composition. As the organic solvent contained in the resin composition, a known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used. When the protective layer is formed by a chemical vapor deposition method, a known chemical vapor deposition method (thermal chemical vapor deposition method, plasma chemical vapor deposition method, or photochemical vapor deposition method) can be used as the chemical vapor deposition method.

The protective layer may contain additives such as organic and inorganic fine particles, absorbers of specific wavelengths (for example, ultraviolet rays, near infrared rays, and the like), refractive index modifiers, antioxidants, adhesives, and surfactants, as necessary. Examples of the organic and inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, calcium carbonate, barium sulfate, and the like. As the absorber of a specific wavelength, a known absorber can be used. Examples of the ultraviolet absorber and the near-infrared absorber include the above-mentioned materials. The content of these additives can be appropriately adjusted, but is preferably 0.1 to 70% by mass, and more preferably 1 to 60% by mass, based on the total mass of the protective layer.

Further, as the protective layer, the protective layer described in paragraphs 0073 to 0092 of japanese patent application laid-open No. 2017-151176 can be used.

< method for manufacturing color filter >

Next, a method for manufacturing a color filter will be described. The color filter of the present invention can be manufactured through the following steps: a step of forming a colored composition layer on a support by using the photosensitive resin composition of the present invention; and forming a pattern on the photosensitive resin composition by photolithography.

The pattern formation by photolithography preferably includes the steps of: a step of forming a photosensitive resin composition layer on a support by using the photosensitive resin composition of the present invention; exposing the photosensitive resin composition layer in a pattern; and a step of forming a pattern (pixel) by removing the unexposed portion of the photosensitive resin composition layer by development. If necessary, a step of baking the photosensitive resin composition layer (pre-baking step) and a step of baking the developed pattern (pixel) (post-baking step) may be provided.

In the step of forming the photosensitive resin composition layer, the photosensitive resin composition layer is formed on the support using the photosensitive resin composition of the present invention. The support is not particularly limited and can be appropriately selected depending on the application. Examples thereof include a glass substrate and a silicon substrate, and a silicon substrate is preferable. Also, a Charge Coupled Device (CCD), a Complementary Metal Oxide Semiconductor (CMOS), a transparent conductive film, and the like may be formed on the substrate. Further, a black matrix for isolating each pixel may be formed on a silicon substrate. Further, an undercoat layer for improving adhesion to the upper layer, preventing diffusion of a substance, or planarizing the substrate surface may be provided on the silicon substrate.

As a method for applying the colored photosensitive composition, a known method can be used. For example, a liquid dropping method (drop casting); slit coating method; spraying; a roll coating method; spin coating (spin coating); tape casting coating method; slit and spin methods; a pre-wet method (e.g., the method described in Japanese patent laid-open No. 2009-145395); various printing methods such as an ink jet method (for example, an on-demand method, a piezoelectric method, a thermal method), discharge printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse set printing, and metal mask printing; a transfer method using a mold or the like; nanoimprint method, and the like. The method of applying the ink jet is not particularly limited, and examples thereof include the methods described in Infinity possibility of ink jet which can be popularized and used, in-2005 2-month release, Sumitbe Techn Research Co., Ltd. (especially, pages 115 to 133), and the methods described in Japanese patent laid-open Nos. 2003-262716, 2003-185831, 2003-261827, 2012-126830, and 2006-1692525. As a method for applying the photosensitive resin composition, the methods described in international publication nos. 2017/030174 and 2017/018419 can be used, and these contents are incorporated in the present specification.

The photosensitive resin composition layer formed on the support may be dried (prebaked). In the case of manufacturing a cured film by a low-temperature process, pre-baking may also be performed. When the prebaking is performed, the prebaking temperature is preferably 150 ℃ or lower, more preferably 120 ℃ or lower, and further preferably 110 ℃ or lower. The lower limit may be, for example, 50 ℃ or higher, or 80 ℃ or higher. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. The prebaking can be performed in a hot plate, oven, or the like.

Next, the photosensitive resin composition layer is exposed in a pattern (exposure step). For example, the photosensitive resin composition layer can be exposed in a pattern form by exposing the photosensitive resin composition layer through a mask having a predetermined mask pattern by using a stepper, a scanner, or the like. Thereby, the exposed portion can be cured.

Examples of the radiation (light) that can be used for exposure include g-rays and i-rays. Light having a wavelength of 300nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300nm or less include KrF rays (wavelength: 248nm) and ArF rays (wavelength: 193nm), and KrF rays (wavelength: 248nm) are preferable. Further, a light source having a long wavelength of 300nm or more can be used.

In the exposure, the exposure may be performed by continuously irradiating light, or may be performed by pulse irradiation (pulse exposure). The pulse exposure refers to a method of repeating irradiation and pause of light in a short period of time (for example, millisecond order or less) to perform exposureThe exposure method of (1). In the pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 ns or less, and further preferably 30 ns or less. The lower limit of the pulse width is not particularly limited, but may be 1 femtosecond (fs) or more, or 10 femtoseconds or more. The frequency is preferably 1kHz or more, more preferably 2kHz or more, and still more preferably 4kHz or more. The upper limit of the frequency is preferably 50kHz or less, more preferably 20kHz or less, and further preferably 10kHz or less. The maximum instantaneous illumination is preferably 50000000W/m²Above, more preferably 100000000W/m²The above is more preferably 200000000W/m²The above. Further, the upper limit of the maximum instantaneous illuminance is preferably 1000000000W/m²Hereinafter, it is more preferably 800000000W/m²Hereinafter, it is more preferably 500000000W/m²The following. In addition, the pulse width refers to the time during which light is irradiated in the pulse period. And, the frequency means the number of pulse periods per 1 second. The maximum instantaneous illuminance is an average illuminance over the time period during which light is irradiated in the pulse period. The pulse period is a period in which the irradiation and pause of light in the pulse exposure are 1 period.

The dose (exposure) is preferably 0.03 to 2.5J/cm²More preferably 0.05 to 1.0J/cm². The oxygen concentration at the time of exposure can be appropriately selected, and in addition to exposure to the atmosphere, exposure to the atmosphere may be performed in a low oxygen environment (for example, 15 vol%, 5 vol%, substantially no oxygen, etc.) in which the oxygen concentration is 19 vol% or less, or exposure to the atmosphere in a high oxygen environment (for example, 22 vol%, 30 vol%, 50 vol%, etc.) in which the oxygen concentration exceeds 21 vol%. The exposure illuminance can be set as appropriate, and can be usually set from 1000W/m²～100000W/m²(e.g., 5000W/m)²、15000W/m²Or 35000W/m²) Selecting the range of (1). The oxygen concentration and the exposure illuminance may be set to an appropriate combination of conditions, for example, an oxygen concentration of 10 vol% and an illuminance of 10000W/m²An oxygen concentration of 35 vol% and an illuminance of 20000W/m²And the like.

Then, the unexposed portions of the photosensitive resin composition layer are removed by development to form a pattern (pixel). The unexposed portions of the photosensitive resin composition layer can be removed by development using a developer. In this way, the photosensitive resin composition layer in the unexposed portion in the exposure step is dissolved in the developer, and only the photocured portion remains. The temperature of the developing solution is preferably 20 to 30 ℃. The developing time is preferably 20 to 180 seconds. In order to improve the residue removal performance, the process of throwing off the developer every 60 seconds and then supplying a new developer may be repeated a plurality of times.

The developer includes an organic solvent, an alkaline developer, and the like, and the alkaline developer is preferably used. As the alkaline developer, an alkaline aqueous solution (alkaline developer) of an alkaline agent is preferably diluted with pure water. Examples of the alkali agent include organic basic compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, and 1, 8-diazabicyclo [5.4.0] -7-undecene, and inorganic basic compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. The alkali agent is preferably a compound having a relatively large molecular weight from the viewpoint of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The developer may further contain a surfactant. The surfactant includes the above-mentioned surfactants, and preferably a nonionic surfactant. From the viewpoint of convenience in transportation and storage, the developer may be temporarily prepared as a concentrated solution and diluted to a desired concentration when used. The dilution ratio is not particularly limited, and may be set, for example, in the range of 1.5 to 100 times. Further, it is also preferable to perform cleaning (rinsing) with pure water after development. It is preferable that the developing photosensitive resin composition layer is washed by supplying a washing liquid to the developing photosensitive resin composition layer while rotating the support on which the developing photosensitive resin composition layer is formed. It is also preferable that the rinsing is performed by moving a nozzle for discharging the rinsing liquid from the center of the support to the peripheral edge of the support. In this case, the nozzle may be moved while gradually decreasing the moving speed of the nozzle when moving from the center portion to the peripheral portion of the support body of the nozzle. By performing flushing in this way, in-plane variations in flushing can be suppressed. Further, the same effect can be obtained by gradually decreasing the rotation speed of the support body while moving the nozzle from the center portion to the peripheral portion of the support body.

After the development, the additional exposure treatment and the heating treatment (post-baking) are preferably performed after the drying. The additional exposure treatment and the post-baking are post-development curing treatments for complete curing. The heating temperature in the post-baking is, for example, preferably 100 to 240 ℃, more preferably 200 to 240 ℃. The post-baking can be performed continuously or intermittently on the developed film by using a heating mechanism such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so as to satisfy the above conditions. When the additional exposure treatment is performed, the light used for the exposure is preferably light having a wavelength of 400nm or less. The additional exposure treatment can be performed by the method described in Korean laid-open patent publication No. 10-2017-0122130.

< solid-state imaging element >

The solid-state imaging element of the present invention has the cured film of the present invention. As a preferred embodiment of the solid-state imaging device, there is mentioned a mode in which the cured film of the present invention is a cyan pixel and further includes a yellow pixel and a magenta pixel.

The structure of the solid-state imaging device of the present invention is not particularly limited as long as it has the cured film of the present invention and functions as a solid-state imaging device, and examples thereof include the following structures.

The structure of the imaging element is as follows: the substrate has a transfer electrode made of polysilicon or the like and a plurality of photodiodes constituting a light receiving region of a solid-state imaging device (a CCD (charge coupled device) image sensor, a CMOS (complementary metal oxide semiconductor) image sensor, or the like), the photodiodes and the transfer electrode have a light shielding film with openings only for light receiving portions of the photodiodes, the light shielding film has a device protection film made of silicon nitride or the like and formed so as to cover the entire surface of the light shielding film and the light receiving portions of the photodiodes, and the device protection film has a color filter. Further, a structure having a light condensing mechanism (for example, a microlens or the like) on the device protective film and on the lower side (side close to the substrate) of the color filter, a structure having a light condensing mechanism on the color filter, or the like may be employed. Also, the color filter may have the following structure: the structure is such that each colored pixel is embedded in a space partitioned by a partition wall, for example, in a lattice shape. The refractive index of the partition at this time is preferably lower than the refractive index of each colored pixel. Examples of image pickup apparatuses having such a configuration include those described in japanese patent laid-open nos. 2012 and 227478, 2014 and 179577, international publication No. 2018/043654, and U.S. patent application publication No. 2018/0040656. The imaging device including the solid-state imaging element of the present invention can be used as a digital camera and an electronic device (such as a mobile phone) having an imaging function, and can also be used as an in-vehicle video camera and a surveillance camera.

< image display device >

The image display device of the present invention has the cured film of the present invention described above. Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. Definitions of image display devices and details of the respective image display devices are described in, for example, "electronic display devices (published in Kogyo chosaai Publishing co., ltd. 1990)," display devices (published in yobo, Sangyo Tosho Publishing co., ltd., 1989), and the like. The liquid crystal display device is described in, for example, "next generation liquid crystal display technology (edited by tianda dragon man, Kogyo chosaai Publishing co., ltd., 1994)"). The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, liquid crystal display devices of various types described in the "next generation liquid crystal display technology" described above.

Examples

The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, processing contents, processing steps and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below.

< measurement of weight average molecular weight (Mw) >)

The weight average molecular weight (Mw) of the resin was measured by Gel Permeation Chromatography (GPC) under the following conditions.

The types of the pipe columns are as follows: a pipe column formed by connecting TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000 and TOSOH TSKgel Super HZ2000

Developing solvent: tetrahydrofuran (THF)

Temperature of the pipe column: 40 deg.C

Flow rate (sample injection amount): 1.0. mu.L (sample concentration 0.1 mass%)

Device name: HLC-8220GPC made by TOSOH CORPORATION

A detector: RI (refractive index) detector

Calibration curve base resin: polystyrene resin

< method for measuring acid value >

The measurement sample was dissolved in a tetrahydrofuran/water 9/1 (mass ratio) mixed solution, and the obtained solution was subjected to neutralization titration with a 0.1mol/L aqueous solution of sodium hydroxide AT 25 ℃ using a potentiometric titrator (product name: AT-510, KYOTO electroinc. The acid value was calculated by the following equation using the inflection point of the titration pH curve as the titration end point.

A＝56.11×Vs×0.1×f/w

A: acid value (mgKOH/g)

Vs: amount of 0.1mol/L aqueous sodium hydroxide solution (mL) required for titration

f: titration amount of 0.1mol/l aqueous solution of sodium hydroxide

w: measuring the mass (g) of the sample (conversion of solid content)

< method for measuring amine number >

The measurement sample was dissolved in acetic acid, and the obtained solution was subjected to neutralization titration with 0.1mol/L perchloric acid/acetic acid solution AT 25 ℃ using a potentiometric titrator (product name: AT-510, KYOTO ELECTRONICS MANUFACTURING CO., LTD.). The amine value was calculated by the following formula using the inflection point of the titration pH curve as the titration end point.

B＝56.11×Vs×0.1×f/w

B: amine number (mgKOH/g)

Vs: the amount of 0.1mol/L perchloric acid/acetic acid solution (mL) required for titration

f: titration amount of 0.1mol/L perchloric acid/acetic acid solution

w: measuring the mass (g) of the sample (conversion of solid content)

< method for measuring average secondary particle diameter of pigment >

As for the average secondary particle diameter of the pigment, the size of the secondary particles of the pigment was directly measured from an electron micrograph using a Transmission Electron Microscope (TEM) to perform measurement. Specifically, the minor axis diameter and major axis diameter of the secondary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment. Next, for each of the 100 pigments, the volume of each pigment was determined as a cube close to the determined particle diameter, and the volume average particle diameter was defined as the average secondary particle diameter.

< preparation of photosensitive resin composition >

A colorant of the type shown in the following table, a dispersant of the type shown in the following table, and a part of a solvent of the type shown in the following table were mixed, 230 parts by mass of zirconia beads having a diameter of 0.3mm were added, dispersion treatment was performed for 5 hours using a paint shaker, and the beads were separated by filtration, thereby producing a pigment dispersion liquid having a solid content of 20 wt%.

Next, the obtained pigment dispersion liquid, the residual solvent of the type described in the following table, the post-addition resin of the type described in the following table, the polymerizable compound of the type described in the following table, the photopolymerization initiator of the type described in the following table, and the ultraviolet absorber of the type described in the following table were mixed to prepare a photosensitive resin composition. The amounts of the respective components blended in the photosensitive resin compositions are shown in the following tables. The numerical values of the respective components are parts by mass. Meanwhile, the total content (mass%) of c.i. pigment blue 15:3(PB15:3) and c.i. pigment blue 15:4(PB15:4) in the colorant, the content (mass%) of the ultraviolet absorber in the total solid content of the photosensitive composition, the content (mass part) of the ultraviolet absorber with respect to 100 mass parts of the photopolymerization initiator, and the content (mass part) of the ultraviolet absorber with respect to 100 mass parts of the polymerizable compound are shown. The Yellow compositions and Magenta compositions shown in the following tables are photosensitive resin compositions for color mixture evaluation, which will be described later.

[ Table 1]

[ Table 2]

In the above tables, the raw materials are abbreviated as follows.

(coloring agent)

PB15: 3: C.I. pigment blue 15:3 (average secondary particle diameter 68nm)

PB15: 4: C.I. pigment blue 15:4 (average secondary particle diameter 71nm)

PcAl: a compound having the following structure (aluminum phthalocyanine, average secondary particle diameter 94nm)

[ chemical formula 26]

PY 150: C.I. pigment yellow 150 (average secondary particle diameter 81nm)

PG 7: C.I. pigment Green 7 (average secondary particle diameter 80nm)

PR 122: C.I. pigment Red 122 (average secondary particle size 67nm)

(dispersant, post resin)

P1: DISPERBYK-2001 (manufactured by BYK Japan K.K., acid value 19mgKOH/g, amine value 29mgKOH/g, acrylic resin)

P2: efka PX 4300 (manufactured by BASF corporation, amine number 57mgKOH/g, acrylic resin)

P3: a resin having the following structure (weight average molecular weight: 10000, acid value: 31.5mgKOH/g, amine value: 0mgKOH/g, and number marked on the main chain represents the molar ratio of the repeating unit.)

[ chemical formula 27]

P4: a resin having the following structure (weight average molecular weight 24000, acid value 52.5mgKOH/g, amine value 0mgKOH/g, number marked on the main chain indicating the molar ratio of the repeating units, number marked on the side chain indicating the number of the repeating units.)

[ chemical formula 28]

P5 resin (weight average molecular weight 21000, acid value 36.0mgKOH/g, amine value 47mgKOH/g, x 48, y 12, a/b/c/d/e 36/4/35/1/24 (molar ratio))

[ chemical formula 29]

P6: a resin having the following structure (weight average molecular weight: 12000, acid value 195.4mgKOH/g, amine value 0mgKOH/g, and number marked on the main chain representing the molar ratio of the repeating units.)

[ chemical formula 30]

(polymerizable Compound)

M1: a compound of the structure

[ chemical formula 31]

M2: a mixture of compounds of the following structure (left compound: right compound: 7:3 (mass ratio))

[ chemical formula 32]

M3: a compound of the structure (l + m + n + o + p + q ═ 12)

[ chemical formula 33]

M4: a compound of the structure

[ chemical formula 34]

(photopolymerization initiator)

I1: a compound of the following structure (alpha-aminoketone compound)

I2: a compound of the structure (oxime compound)

[ chemical formula 35]

(ultraviolet absorber)

U1: a compound (conjugated diene compound) having the following structure

U2: a compound (triazine compound) of the following structure

U3: a compound of the structure (benzotriazole compound)

[ chemical formula 36]

(surfactant)

W1: a compound having the following structure (fluorine-based surfactant, weight average molecular weight 14000, and% representing the proportion of the repeating unit is mol%)

[ chemical formula 37]

(other additives)

X1: 1, 2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol (Compound of the following Structure, epoxy Compound)

[ chemical formula 38]

X2: a compound (silane coupling agent) of the following structure

[ chemical formula 39]

(solvent)

S1: propylene glycol monomethyl ether acetate

S2: propylene glycol monomethyl ether

< evaluation >

(evaluation of spectral characteristics of cyan)

The photosensitive resin composition was applied to a glass substrate by a spin coating method, followed by heat treatment (prebaking) at 100 ℃ for 120 seconds using a hot plate, followed by irradiation with i-rays at 1000mJ/cm²The film was exposed to light at the exposure dose of (1) and then heated at 200 ℃ for 5 minutes to prepare a cured film having a thickness of 0.6. mu.m. As the obtained cured film, use was made of OTSUKA ELECTRONICS Co., manufactured by LTD, MCPD-3000, forThe light transmittance (transmittance) was measured in the range of 400 to 700 nm. When the average transmittance at 400 to 530nm was T1, the average transmittance at 610 to 700nm was T2, and the 50% transmittance was λ 50, the spectral characteristics as cyan were determined by the following criteria. A case where all of the following items 3 are satisfied is assumed as a, a case where only the item 2 is satisfied is assumed as B, a case where only the item 1 is satisfied is assumed as C, and a case where none of the items is satisfied is assumed as D.

T1 is 70% or more.

T2 is 30% or less.

λ 50 is in the range of 540 to 590 nm.

(evaluation of light resistance)

The photosensitive resin composition was applied to a glass substrate by a spin coating method, followed by heat treatment (prebaking) at 100 ℃ for 120 seconds using a hot plate, followed by irradiation with i-rays at 1000mJ/cm²The film was exposed to light at the exposure dose of (1) and then heated at 200 ℃ for 5 minutes to prepare a cured film having a thickness of 0.6. mu.m. Regarding the obtained cured film, light transmittance (transmittance) in a wavelength range of 400 to 700nm was measured using MCPD-3000 manufactured by OTSUKA ELECTRONICS co. Subsequently, the cured film prepared in the above was irradiated with 100000Lux of light (total irradiation amount: 1 hundred million Lux hr) for 1000 hours by a light resistance tester (Super Xenon Weather Meter SX75, manufactured by Suga Test Instruments co., ltd.). The transmittance of the cured film after light irradiation was measured, and the light resistance was evaluated by the following criteria.

A: the integrated value of the transmittance of the cured film at the wavelength of 400-700 nm after the light irradiation is more than 97% of the integrated value of the transmittance of the cured film at the wavelength of 400-700 nm before the light irradiation.

B: the integrated value of the transmittance of the cured film at the wavelength of 400-700 nm after the light irradiation is 95% or more and less than 97% of the integrated value of the transmittance of the cured film at the wavelength of 400-700 nm before the light irradiation.

C: the integrated value of the transmittance of the cured film at the wavelength of 400-700 nm after the light irradiation is less than 95% of the integrated value of the transmittance of the cured film at the wavelength of 400-700 nm before the light irradiation.

(evaluation of rectangularity)

A silicon wafer having a diameter of 8 inches (1 inch ═ 25.4mm) was subjected to a heat treatment in an oven at 200 ℃ for 30 minutes. Next, a resist liquid for undercoating (CT-4000, manufactured by FUJIFILM Electronic Materials co., ltd.) was applied onto the silicon wafer so that the dry film thickness became 0.1 μm, and further, the silicon wafer was heated and dried in an oven at 220 ℃ for 1 hour to form an undercoating layer, thereby obtaining a silicon wafer substrate with an undercoating layer.

The photosensitive resin composition was coated on the undercoat layer of the silicon wafer substrate with an undercoat layer prepared in the above. Subsequently, heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 ℃. Next, an i-ray step exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used at a wavelength of 365nm at 500mJ/cm through a mask having a pattern²The exposure was carried out at the same time. The mask used was a mask having an island pattern of 1.4 μm × 1.4 μm.

Next, the substrate on which the irradiated coating film was formed was placed on a horizontal turntable of a rotary spray developing machine (DW-30 model, manufactured by chemtronics co., ltd.) and subjected to spin immersion development for 60 seconds at room temperature using an alkaline developing solution (CD-2060, manufactured by FUJIFILM Electronic Materials co., ltd.). Next, the substrate after the spin-on immersion development was fixed to a horizontal turntable by a vacuum chuck method, and while the silicon wafer was rotated at a rotation speed of 50rpm by a rotating device, pure water was supplied in a shower-like manner from a nozzle from above the rotation center thereof to perform a rinsing process (23 seconds × 2 times), followed by spin drying, and then a heating process (post-baking) was performed at 200 ℃ for 300 seconds by using a hot plate, thereby forming a pattern (pixel) of a cured film.

The obtained cured film was cut into a pattern, and the cross section of the pattern of the cured film was observed at 20000 times magnification using a Scanning Electron Microscope (SEM), and the rectangularity was evaluated by the following criteria.

A: the width of the surface of the substrate side (side in contact with the substrate) of the pattern of the cured film is 90% to 130% of the width of the surface on the side opposite to the substrate.

B: the width of the surface of the substrate side (side in contact with the substrate) of the pattern of the cured film is 80% or more and less than 90% or more and 130% or less than 160% of the width of the surface on the side opposite to the substrate.

C: the width of the surface of the substrate side (side in contact with the substrate) of the pattern of the cured film is less than 80% or 160% or more of the width of the surface on the side opposite to the substrate. Alternatively, the cured film cannot be patterned due to peeling caused by development.

(evaluation of defects)

A silicon wafer having a diameter of 8 inches (1 inch ═ 25.4mm) was subjected to a heat treatment in an oven at 200 ℃ for 30 minutes. Next, a resist liquid for undercoating (CT-4000, manufactured by FUJIFILM Electronic Materials co., ltd.) was applied onto the silicon wafer so that the dry film thickness became 0.1 μm, and further, the silicon wafer was heated and dried in an oven at 220 ℃ for 1 hour to form an undercoating layer, thereby obtaining a silicon wafer substrate with an undercoating layer.

The photosensitive resin composition was coated on the undercoat layer of the silicon wafer substrate with an undercoat layer prepared in the above. Subsequently, heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 ℃. Next, an i-ray step exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used at a wavelength of 365nm at 500mJ/cm through a mask having a pattern²The exposure was carried out at the same time. The mask used was capable of forming an island pattern of 1.4 μm × 1.4 μm at a period of 2.8 μm × 2.8 μm, and the entire area of the wafer excluding the outer periphery by 3mm was exposed with a lens of 11mm × 11mm size.

Next, the substrate on which the irradiated coating film was formed was placed on a horizontal turntable of a rotary spray developing machine (DW-30 model, manufactured by chemtronics co., ltd.) and subjected to spin immersion development for 60 seconds at room temperature using an alkaline developing solution (CD-2060, manufactured by FUJIFILM Electronic Materials co., ltd.). Next, the substrate after the spin-on immersion development was fixed to a horizontal turntable by a vacuum chuck method, and while the silicon wafer was rotated at a rotation speed of 50rpm by a rotating device, pure water was supplied in a shower-like manner from a nozzle from above the rotation center thereof to perform a rinsing process (23 seconds × 2 times), followed by spin drying, and then a heating process (post-baking) was performed at 200 ℃ for 300 seconds by using a hot plate, thereby forming a pattern (pixel) of a cured film. The obtained cured film was inspected for the number of defects in the pattern using a wafer defect evaluation apparatus (manufactured by ComPLUS3, AMAT). The defects were evaluated by the following criteria.

A: total defect number in 8-inch wafer is less than or equal to 30

B: total defect number in 30-8 inch wafer is less than or equal to 100

C: total number of defects in 100 < 8 inch wafer

(evaluation of color mixture)

The photosensitive resin composition was coated on a silicon wafer having a diameter of 8 inches (1 inch: 25.4 mm). Subsequently, heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 ℃. Next, using an i-ray step exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) at a wavelength of 365nm at 500mJ/cm²The exposure was carried out at the same time. The mask used was a mask having an island pattern of 2cm × 2 cm. Next, the substrate on which the irradiated coating film was formed was placed on a horizontal turntable of a rotary spray developing machine (DW-30 model, manufactured by chemtronics co., ltd.) and subjected to spin immersion development for 60 seconds at room temperature using an alkaline developing solution (CD-2060, manufactured by FUJIFILM Electronic Materials co., ltd.). Next, the substrate after the spin-on immersion development was fixed to a horizontal turntable by a vacuum chuck method, and while the silicon wafer was rotated at a rotation speed of 50rpm by a rotating device, pure water was supplied in a shower-like manner from a nozzle from above the rotation center thereof to perform a rinsing process (23 seconds × 2 times), followed by spin drying, and then a heating process (post-baking) was performed at 200 ℃ for 300 seconds by using a hot plate, thereby forming a pattern of a cured film.

Regarding the pattern of the obtained cured film, light transmittance (transmittance) in the wavelength range of 400 to 700nm was measured using MCPD-3000 manufactured by Otsuka Electronics co., ltd.

Subsequently, the photosensitive resin composition for color mixture evaluation was spin-coated on the pattern of the cured film prepared above, and heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ℃. The Yellow composition and Magenta composition described above were used as the photosensitive resin composition for color mixture evaluation.

Next, the substrate on which the coating film of the photosensitive resin composition for color mixture evaluation was formed was placed on a horizontal turntable of a rotary spray developing machine (DW-30 type, chemical Materials co., ltd., manufactured), and subjected to spin-on immersion development for 60 seconds at room temperature using an alkaline developing solution (CD-2060, FUJIFILM Electronic Materials co., ltd., manufactured), thereby peeling off the coating film of the photosensitive resin composition for color mixture evaluation. Next, the substrate after the spin-on immersion development was fixed to a horizontal turntable by a vacuum chuck system, and while the silicon wafer was rotated at a rotation speed of 50rpm by a rotating device, pure water was supplied in a shower-like manner from a nozzle from above the rotation center thereof to perform a rinsing treatment (23 seconds × 2 times), followed by spin-drying, and a color mixture evaluation test was performed.

Regarding the pattern of the cured film after the color mixture evaluation test, the amount of change in the integrated value of the transmittance was determined by measuring the light transmittance (transmittance) at a wavelength in the range of 400 to 700nm using MCPD-3000 manufactured by Otsuka Electronics co.

A: the change amount of the integrated value of the transmittance is less than 1%

B: the variation of the integrated value of the transmittance is 1% or more and less than 1.5%

C: the variation of the integrated value of the transmittance is 1.5% or more

[ Table 3]

[ Table 4]

[ Table 5]

As shown in the above table, in the examples, the evaluation of the spectral characteristics, light resistance and color mixture as cyan was excellent.

(example 100)

The Cyan composition was applied to a silicon wafer by a spin coating method so that the film thickness after film formation became 1.0. mu.m. Next, the plate was heated at 100 ℃ for 2 minutes using a hot plate. Next, an i-ray step exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used at 1000mJ/cm²The exposure was performed through a 2 μm square dot pattern mask. Then, spin-immersion development was performed at 23 ℃ for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, the film was washed by spin-spray rinsing and further washed with pure water. Next, the Cyan composition was patterned by heating at 200 ℃ for 5 minutes using a hot plate. Similarly, the Yellow composition and Magenta composition were patterned in this order to form cyan, Yellow, and Magenta colored patterns (bayer pattern), thereby producing a color filter.

The photosensitive resin composition of example 2 was used as the Cyan composition.

The Yellow composition and the Magenta composition were used as the Yellow composition and the Magenta composition, respectively.

The obtained color filter is embedded in a solid-state imaging element according to a known method. The solid-state imaging element has an appropriate image recognition capability.