阅读说明：本技术 感光性组合物 (Photosensitive composition ) 是由 大河原昂广 奈良裕树 中村翔一 吉林光司 于 2019-02-13 设计创作，主要内容包括：一种感光性组合物,其用于脉冲曝光且包含色材A、光引发剂B及与由光引发剂B产生的活性种进行反应而固化的化合物C,光引发剂B包含满足下述条件1的光引发剂b1,条件1：在最大瞬间照度375000000W/m<Sup>2</Sup>、脉冲宽度8纳秒、频率10Hz的条件下,对包含0.035mmol/L光引发剂b1的丙二醇单甲醚乙酸酯溶液脉冲曝光波长355nm的光之后的量子产率q<Sub>355</Sub>为0.05以上。(A photosensitive composition for pulse exposure, which comprises a color material A, a photoinitiator B and a compound that is cured by reacting with an active species generated by the photoinitiator BCompound C, photoinitiator B comprises photoinitiator B1 satisfying the following condition 1, condition 1: at the maximum instant of the illuminance 375000000W/m 2 The quantum yield q after pulse exposure of a propylene glycol monomethyl ether acetate solution containing 0.035mmol/L of photoinitiator b1 to light having a wavelength of 355nm under conditions of a pulse width of 8 ns and a frequency of 10Hz 355 Is 0.05 or more.)

1. A photosensitive composition for pulse exposure, which comprises a color material A, a photoinitiator B, and a compound C that is cured by reaction with an active species generated by the photoinitiator B,

the photoinitiator B comprises a photoinitiator B1 satisfying the following condition 1,

condition 1: at the maximum instant of the illuminance 375000000W/m²The quantum yield q after pulse exposure of a propylene glycol monomethyl ether acetate solution containing 0.035mmol/L of photoinitiator b1 to light having a wavelength of 355nm under conditions of a pulse width of 8 ns and a frequency of 10Hz₃₅₅Is 0.05 or more.

2. The photosensitive composition according to claim 1, wherein,

quantum yield q of the photoinitiator b1₃₅₅Is 0.10 or more.

3. The photosensitive composition for pulse exposure according to claim 1, wherein,

the photoinitiator b1 satisfies the following condition 2,

condition 2: at the maximum instant of the illuminance 375000000W/m²The quantum yield q after pulse exposure of light having a wavelength of 265nm to a film having a thickness of 1.0 μm and containing 5% by mass of photoinitiator b1 and 95% by mass of resin under conditions of a pulse width of 8 ns and a frequency of 10Hz₂₆₅Is 0.05 or more.

4. The photosensitive composition according to claim 3, wherein,

quantum yield q of the photoinitiator b1₂₆₅Is 0.10 or more.

5. The photosensitive composition according to any one of claims 1 to 4, wherein,

the photoinitiator b1 satisfies the following condition 3,

condition 3: at the maximum instant of the illuminance 625000000W/m²A film containing 5% by mass of a photoinitiator b1 and a resin is exposed to light having a wavelength within the range of 248 to 365nm in a 1-pulse manner under the conditions of a pulse width of 8 ns and a frequency of 10Hz, and the concentration of active species in the film is 1cm per unit²The film is more than 0.000000001 mmol.

6. The photosensitive composition according to claim 5, wherein,

in the photoinitiator b1, the film in the condition 3The concentration of active species in the culture medium reaches every 1cm²The film thickness was 0.0000001mmol or more.

7. The photosensitive composition according to claim 5 or 6,

the photoinitiator B comprises 2 or more photoinitiators and satisfies the following condition 3a,

condition 3 a: at the maximum instant of the illuminance 625000000W/m²A film containing 5% by mass of the mixture and the resin is subjected to pulse exposure for 0.1 second to light having a wavelength within a range of 248 to 365nm under conditions of a pulse width of 8 ns and a frequency of 10Hz, and the concentration of active species in the film reaches 1cm per 1cm²And a film of 0.000000001mmol or more, wherein 2 or more kinds of photoinitiators are mixed in the mixture in a ratio contained in the photosensitive composition.

8. The photosensitive composition according to any one of claims 1 to 7, wherein,

the photoinitiator B is a photo-radical polymerization initiator, and the compound C is a radical polymerizable compound.

9. The photosensitive composition according to any one of claims 1 to 8, wherein,

the compound C contains a radically polymerizable monomer having 2 or more functions.

10. The photosensitive composition according to any one of claims 1 to 9, wherein,

the compound C contains a radical polymerizable monomer having a fluorene skeleton.

11. The photosensitive composition according to any one of claims 1 to 10, wherein,

the content of the color material A in the total solid content of the photosensitive composition is 40 mass% or more.

12. The photosensitive composition according to any one of claims 1 to 11,

the content of the photoinitiator B in the total solid content of the photosensitive composition is 15 mass% or less.

13. The photosensitive composition according to any one of claims 1 to 12, wherein,

the content of the photoinitiator B in the total solid content of the photosensitive composition is 7 mass% or less.

14. The photosensitive composition according to any one of claims 1 to 13, further comprising a silane coupling agent.

15. The photosensitive composition according to any one of claims 1 to 14, which is a photosensitive composition for pulse exposure using light having a wavelength of 300nm or less.

16. The photosensitive composition according to any one of claims 1 to 15, which is for use in producing a maximum instantaneous illuminance of 50000000W/m²A photosensitive composition subjected to pulse exposure under the above conditions.

17. The photosensitive composition according to any one of claims 1 to 16, which is a photosensitive composition for a solid-state image pickup element.

18. The photosensitive composition according to any one of claims 1 to 17, which is a photosensitive composition for color filters.

Technical Field

The present invention relates to a photosensitive composition containing a color material. More specifically, the present invention relates to a photosensitive composition used for a solid-state imaging device, a color filter, or the like.

Background

A solid-state image sensor such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor) is used in a video camera, a digital camera, a mobile phone with an image pickup function, and the like. In addition, a film containing a color material such as a color filter is used for the solid-state imaging element. A film containing a color material such as a color filter can be produced using, for example, a photosensitive composition containing a color material, a radical polymerizable monomer, and a photo radical polymerization initiator (see patent documents 1 and 2).

Prior art documents

Patent document

Patent document 1: japanese Kohyo publication No. 2012-532334

Patent document 2: japanese patent application laid-open No. 2010-097172

Disclosure of Invention

Technical problem to be solved by the invention

In the case of a film containing a color material, if the film is insufficiently cured, the color material flows out of the film and the color is transferred to another film. Therefore, when a film containing a color material is produced, it is necessary to produce a sufficiently cured film. Therefore, in recent years, further improvement in curability has been desired for a photosensitive composition containing a color material.

Accordingly, an object of the present invention is to provide a photosensitive composition having excellent curability.

Means for solving the technical problem

The present inventors have conducted intensive studies on a photosensitive composition, and as a result, have found that a film which is excellent in curability and sufficiently cured can be formed after exposure of the photosensitive composition to pulse exposure, thereby completing the present invention. Accordingly, the present invention provides the following.

< 1 > a photosensitive composition for pulse exposure comprising a color material A, a photoinitiator B and a compound C which is cured by reaction with active species generated by the photoinitiator B,

the photoinitiator B comprises a photoinitiator B1 satisfying the following condition 1,

condition 1: at the maximum instant of the illuminance 375000000W/m²The quantum yield q after pulse exposure of a propylene glycol monomethyl ether acetate solution containing 0.035mmol/L of photoinitiator b1 to light having a wavelength of 355nm under conditions of a pulse width of 8 ns and a frequency of 10Hz₃₅₅Is 0.05 or more.

< 2 > the photosensitive composition according to < 1 >, wherein,

quantum yield q of photoinitiator b1₃₅₅Is 0.10 or more.

< 3 > the photosensitive composition according to < 1 >, wherein,

the photoinitiator b1 satisfies the following condition 2,

condition 2: at the maximum instant of the illuminance 375000000W/m²The quantum yield q after pulse exposure of light having a wavelength of 265nm to a film having a thickness of 1.0 μm and containing 5% by mass of photoinitiator b1 and 95% by mass of resin under conditions of a pulse width of 8 ns and a frequency of 10Hz₂₆₅Is 0.05 or more.

< 4 > the photosensitive composition according to the above, wherein,

quantum yield q of photoinitiator b1₂₆₅Is 0.10 or more.

< 5 > the photosensitive composition according to any one of < 1 > to < 4 >, wherein,

the photoinitiator b1 satisfies the following condition 3,

condition 3: at the maximum instant of the illuminance 625000000W/m²And a film containing 5% by mass of a photoinitiator b1 and a resin is exposed to light at a pulse exposure wavelength of 1 pulse within a range of 248 to 365nm under conditions of a pulse width of 8 ns and a frequency of 10HzAfter one wavelength of light, the concentration of active species in the film reaches every 1cm²The film is more than 0.000000001 mmol.

< 6 > the photosensitive composition according to < 5 >, wherein,

in the photoinitiator b1, the concentration of active species in the film in condition 3 reached every 1cm²The film thickness was 0.0000001mmol or more.

< 7 > the photosensitive composition according to < 5 > or < 6 >, wherein,

the photoinitiator B contains 2 or more photoinitiators and satisfies the following condition 3a,

condition 3 a: at the maximum instant of the illuminance 625000000W/m²A film containing 5 mass% of a resin and a mixture containing 2 or more photoinitiators in a proportion contained in a photosensitive composition, the film having a pulse width of 8 ns and a frequency of 10Hz, and the film being subjected to pulse exposure for 0.1 second to light having a wavelength within a range of 248 to 365nm, wherein the concentration of active species in the film is 1cm per 1cm²The film is more than 0.000000001 mmol.

< 8 > the photosensitive composition according to any one of < 1 > to < 7 >, wherein,

the photoinitiator B is a photo radical polymerization initiator, and the compound C is a radical polymerizable compound.

< 9 > the photosensitive composition according to any one of < 1 > to < 8 >, wherein,

the compound C contains a radically polymerizable monomer having 2 or more functions.

< 10 > the photosensitive composition according to any one of < 1 > to < 9 >, wherein,

the compound C contains a radical polymerizable monomer having a fluorene skeleton.

< 11 > the photosensitive composition according to any one of < 1 > to < 10 >, wherein,

the content of the color material A in the total solid content of the photosensitive composition is 40 mass% or more.

< 12 > the photosensitive composition according to any one of < 1 > to < 11 >, wherein,

the content of the photoinitiator B in the total solid content of the photosensitive composition is 15 mass% or less.

< 13 > the photosensitive composition according to any one of < 1 > to < 12 >, wherein,

the content of the photoinitiator B in the total solid content of the photosensitive composition is 7 mass% or less.

< 14 > the photosensitive composition according to any one of < 1 > to < 13 >, wherein,

it further comprises a silane coupling agent.

< 15 > the photosensitive composition according to any one of < 1 > to < 13 >, which is a photosensitive composition for pulse exposure with light having a wavelength of 300nm or less.

< 16 > the photosensitive composition according to any one of < 1 > to < 15 > for the maximum instantaneous illuminance of 50000000W/m²A photosensitive composition subjected to pulse exposure under the above conditions.

< 17 > the photosensitive composition according to any one of < 1 > to < 16 > which is a photosensitive composition for a solid-state image pickup element.

< 18 > the photosensitive composition according to any one of < 1 > to < 17 > which is a photosensitive composition for color filters.

Effects of the invention

According to the present invention, a photosensitive composition having excellent curability can be provided.

Detailed Description

The present invention will be described in detail below.

In the present specification, "to" is used to include numerical values described before and after the "to" as a lower limit value and an upper limit value.

In the labeling of the group (atomic group) in the present specification, the label not labeled with substitution and not substituted includes a group (atomic group) having no substituent and also includes a group (atomic group) having a substituent. 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, "(meth) allyl" represents both or either allyl and methallyl, "(meth) acrylate" represents both or either acrylate and methacrylate, "(meth) acrylic acid" represents both or either acrylic acid and methacrylic acid, and "(meth) acryloyl" represents both or either acryloyl and methacryloyl.

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 term "infrared" refers to light having a wavelength of 700 to 2500 nm.

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

In the present specification, the term "step" includes not only an independent step but also a step that can achieve a desired action of the step even when the step is not clearly distinguished from other steps.

< photosensitive composition >

The photosensitive composition of the present invention is a photosensitive composition for pulse exposure, characterized in that,

the photosensitive composition comprises a color material A, a photoinitiator B and a compound C which reacts with active species generated by the photoinitiator B and is cured,

the photoinitiator B contains a photoinitiator B1 satisfying the following condition 1.

Condition 1: at the maximum instant of the illuminance 375000000W/m²The quantum yield q after pulse exposure of a propylene glycol monomethyl ether acetate solution containing 0.035mmol/L of photoinitiator b1 to light having a wavelength of 355nm under conditions of a pulse width of 8 ns and a frequency of 10Hz₃₅₅Is 0.05 or more.

Since the photoinitiator B included in the photosensitive composition of the present invention includes the photoinitiator B1 satisfying the above condition 1, the compound C can be efficiently cured by instantaneously generating a large amount of active species such as radicals from the photoinitiator B1 by pulse exposure of the photosensitive composition. Therefore, the photosensitive composition of the present invention has excellent curability. The pulse exposure is an exposure method of repeating the irradiation and pause of light in a short period of time (for example, millisecond order or less).

The photosensitive composition of the present invention is a photosensitive composition for pulse exposure. The light used for exposure may be light having a wavelength of more than 300nm or light having a wavelength of 300nm or less, but for the reason of easily obtaining more excellent curability, light having a wavelength of 300nm or less is preferable, light having a wavelength of 270nm or less is more preferable, and light having a wavelength of 250nm or less is even more preferable. The light is preferably light having a wavelength of 180nm or more. Specifically, KrF rays (wavelength 248nm), ArF rays (wavelength 193nm) and the like are mentioned, and KrF rays (wavelength 248nm) are preferred because they facilitate obtaining more excellent curability.

The exposure conditions for the pulse exposure are preferably as follows. The pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 ns or less, and still more preferably 30 ns or less, from the viewpoint of the ease of instantaneously generating a large amount of active species such as radicals. The lower limit of the pulse width is not particularly limited, but may be 1 femtosecond (fs) or more, or 10 femtoseconds or more. From the reason that the compound C is easily thermally polymerized by exposure heat, the frequency is preferably 1kHz or more, more preferably 2kHz or more, and further preferably 4kHz or more. The upper limit of the frequency is preferably 50kHz or less, more preferably 20kHz or less, and still more preferably 10kHz or less, for the reason of easily suppressing deformation of the substrate or the like due to exposure heat. From the viewpoint of curability, the maximum instantaneous illuminance is preferably 50000000W/m²Above, more preferably 100000000W/m²The above is more preferably 200000000W/m²The above. From the viewpoint of suppressing the failure of high illuminance, the upper limit of the maximum instantaneous illuminance is preferably 1000000000W/m²Hereinafter, 800000000W/m is more preferable²Hereinafter, 500000000W/m is more preferable²The following. The pulse width is a length of time during which light is irradiated in a pulse period. And, frequencyThe rate refers to 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 photosensitive composition of the present invention is preferably used as a composition for forming colored pixels, black pixels, barrier films, pixels of infrared transmission filter layers, and the like. Examples of the colored pixels include pixels having hues selected from red, blue, green, cyan, magenta, and yellow. Examples of the pixels of the infrared transmitting filter layer include pixels of a filter layer satisfying spectral characteristics such that the maximum value of the transmittance in the wavelength range of 400 to 640nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1100 to 1300nm is 70% or more (preferably 75% or more, more preferably 80% or more). Further, it is preferable that the pixels of the infrared transmitting filter layer are pixels of a filter layer satisfying any of the following spectral characteristics (1) to (4).

(1): a pixel of a filter layer having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) at a wavelength of 400 to 640nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) at a wavelength of 800 to 1300 nm.

(2): a pixel of a filter layer having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) at a wavelength of 400 to 750nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) at a wavelength of 900 to 1300 nm.

(3): a pixel of a filter layer having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) at a wavelength of 400 to 830nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) at a wavelength of 1000 to 1300 nm.

(4): a pixel of a filter layer having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) at a wavelength of 400 to 950nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) at a wavelength of 1100 to 1300 nm.

When the photosensitive composition of the present invention is used as a composition for forming a pixel of an infrared transmission filter layer, the photosensitive composition of the present invention preferably satisfies spectral characteristics in which the ratio Amin/Bmax of the minimum value Amin of absorbance at a wavelength of 400 to 640nm to the maximum value Bmax of absorbance at a wavelength of 1100 to 1300nm is 5 or more. Amin/Bmax is more preferably 7.5 or more, still more preferably 15 or more, and particularly preferably 30 or more.

The absorbance a λ at an arbitrary wavelength λ is defined by the following formula (1).

Aλ＝-log(Tλ/100)……(1)

A λ is absorbance at the wavelength λ, and T λ is transmittance (%) at the wavelength λ.

In the present invention, the value of absorbance may be a value measured in a state of a solution, or a value measured in a state of a film produced using a photosensitive composition. When the absorbance is measured in the state of a film, it is preferable to measure the absorbance by applying the photosensitive composition on a glass substrate by a method such as spin coating so that the thickness of the dried film becomes a predetermined thickness, and drying the film at 100 ℃ for 120 seconds using a hot plate.

When the photosensitive composition of the present invention is used as a pixel-forming composition for an infrared-transmitting filter layer, the photosensitive composition of the present invention more preferably satisfies any of the following spectral characteristics (11) to (14).

(11): the ratio Amin1/Bmax1 of the minimum value Amin1 of absorbance at a wavelength of 400 to 640nm to the maximum value Bmax1 of absorbance at a wavelength of 800 to 1300nm is 5 or more, preferably 7.5 or more, more preferably 15 or more, and still more preferably 30 or more. According to this embodiment, a film which blocks light having a wavelength in the range of 400 to 640nm and can transmit light having a wavelength of 720nm or more can be formed.

(12): the ratio Amin2/Bmax2 of the minimum value Amin2 of absorbance at a wavelength of 400 to 750nm to the maximum value Bmax2 of absorbance at a wavelength of 900 to 1300nm is 5 or more, preferably 7.5 or more, more preferably 15 or more, and still more preferably 30 or more. According to this embodiment, a film which blocks light having a wavelength in the range of 400 to 750nm and can transmit light having a wavelength of 850nm or more can be formed.

(13): the ratio Amin3/Bmax3 of the minimum value Amin3 of absorbance at a wavelength of 400 to 850nm to the maximum value Bmax3 of absorbance at a wavelength of 1000 to 1300nm is 5 or more, preferably 7.5 or more, more preferably 15 or more, and still more preferably 30 or more. According to this embodiment, a film which blocks light having a wavelength in the range of 400 to 850nm and can transmit light having a wavelength of 940nm or more can be formed.

(14): the ratio Amin4/Bmax4 of the minimum value Amin4 of absorbance at a wavelength of 400 to 950nm to the maximum value Bmax4 of absorbance at a wavelength of 1100 to 1300nm is 5 or more, preferably 7.5 or more, more preferably 15 or more, and still more preferably 30 or more. According to this embodiment, a film which blocks light having a wavelength in the range of 400 to 950nm and can transmit light having a wavelength of 1040nm or more can be formed.

The photosensitive composition of the present invention can be preferably used as a photosensitive composition for a solid-state imaging element. The photosensitive composition of the present invention can be preferably used as a photosensitive composition for color filters. Specifically, the photosensitive composition for forming pixels can be preferably used as a color filter, and more preferably used as a color filter used in a solid-state imaging device.

The respective components used in the photosensitive composition of the present invention will be described below.

Color Material A

The photosensitive composition of the present invention contains a color material a (hereinafter, simply referred to as a color material). Examples of the coloring material include a color colorant, a black colorant, and an infrared absorbing pigment. The color material used in the photosensitive composition of the present invention preferably contains at least a color colorant.

(color colorant)

Examples of the colored colorant include a red colorant, a green colorant, a blue colorant, a yellow colorant, a violet colorant, and an orange colorant. The colored colorant may be a pigment or a dye. Pigments are preferred. The average particle diameter (r) of the pigment is preferably 20 nm. ltoreq. r.ltoreq.300 nm, more preferably 25 nm. ltoreq. r.ltoreq.250 nm, and further preferably 30 nm. ltoreq. r.ltoreq.200 nm. The "average particle diameter" herein refers to an average particle diameter of secondary particles of the primary particles to which the pigment is polymerized. The secondary particles included in the range of the average particle diameter ± 100nm in the particle size distribution (hereinafter, simply referred to as "particle size distribution") of the secondary particles of the pigment that can be used are preferably 70 mass% or more, and more preferably 80 mass% or more of the entire.

The pigment is preferably an organic pigment. The organic pigment may be the following pigments.

Color index (c.i.) Pigment Yellow (Pigment Yellow)1, 2, 3,4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 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, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 187, 188, 193, 188, 194, 185, 194, 199, 214, and the like,

Pigment Orange (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 pigments above),

Pigment Red (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, 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, etc. (Red pigments, supra),

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

C.I. Pigment Violet (Pigment Violet)1, 19, 23, 27, 32, 37, 42, etc. (above: purple Pigment),

C.i. Pigment Blue (Pigment Blue)1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80 etc. (above for Blue pigments).

These organic pigments can be used alone or in combination of plural kinds.

As the yellow pigment, a metal azo pigment containing at least 1 kind of anion selected from an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure thereof, 2 or more kinds of metal ions, and a melamine compound can also be used.

[ chemical formula 1]

In the formula, R¹And R²Are each independently-OH or-NR⁵R⁶，R³And R⁴Each independently is ═ O or ═ NR⁷，R⁵～R⁷Each independently is a hydrogen atom or an alkyl group. R⁵～R⁷The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. The alkyl group may be any of linear, branched and cyclic, and is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent. The substituents are preferably halogen atoms, hydroxyl groups, alkoxy groups, cyano groups and amino groups.

In the formula (I), R¹And R²preferably-OH. And, R³And R⁴Preferably ═ O.

The melamine compound in the metal azo pigment is preferably a compound represented by the following formula (II).

[ chemical formula 2]

In the formula R¹¹～R¹³Each independently is a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear. The alkyl group may have a substituent. The substituent is preferably a hydroxyl group. R¹¹～R¹³At least one of (A) is preferably a hydrogen atom, R¹¹～R¹³All of (3) are more preferably hydrogen atoms.

The above-mentioned metallic azo pigment is preferably an azo pigment containing at least 1 anion selected from the group consisting of the azo compounds represented by the above-mentioned formula (I) and the azo compounds having a tautomeric structure, and containing at least Zn²⁺And Cu²⁺Metal ions and a melamine compound. In this embodiment, the total amount of Zn is preferably 95 to 100 mol% based on 1 mol of the total metal ions of the metal azo pigment²⁺And Cu²⁺More preferably 98 to 100 mol%, still more preferably 99.9 to 100 mol%, and particularly preferably 100 mol%. And, Zn in the metallic azo pigment²⁺And Cu²⁺Is preferably Zn^{2 +}:Cu²⁺199:1 to 1:15, more preferably 19:1 to 1:1, and still more preferably 9:1 to 2: 1. Also, in this mode, the metallic azo pigment may further contain other than Zn²⁺And Cu²⁺Other divalent or trivalent metal ions (hereinafter also referred to as metal ion Me 1). Examples of the metal ion Me1 include Ni²⁺、Al³⁺、Fe²⁺、Fe³⁺、Co²⁺、Co³⁺、La³⁺、Ce³⁺、Pr³⁺、Nd²⁺、Nd³⁺、Sm²⁺、Sm³⁺、Eu²⁺、Eu³⁺、Gd³⁺、Tb³⁺、Dy³⁺、Ho³⁺、Yb²⁺、Yb³⁺、Er³⁺、Tm³⁺、Mg²⁺、Ca²⁺、Sr²⁺、Mn²⁺、Y³⁺、Sc³⁺、Ti²⁺、Ti³⁺、Nb³⁺、Mo²⁺、Mo³⁺、V²⁺、V³⁺、Zr²⁺、Zr³⁺、Cd²⁺、Cr³⁺、Pb²⁺、Ba²⁺Preferably selected from Al³⁺、Fe²⁺、Fe³⁺、Co²⁺、Co³⁺、La³⁺、Ce³⁺、Pr³⁺、Nd³⁺、Sm³⁺、Eu³⁺、Gd³⁺、Tb³⁺、Dy³⁺、Ho³⁺、Yb³⁺、Er³⁺、Tm³⁺、Mg²⁺、Ca²⁺、Sr^{2 +}、Mn²⁺And Y³⁺More preferably at least 1 selected from Al³⁺、Fe²⁺、Fe³⁺、Co²⁺、Co³⁺、La³⁺、Ce³⁺、Pr³⁺、Nd³⁺、Sm³⁺、Tb³⁺、Ho³⁺And Sr²⁺At least 1, particularly preferably selected from Al³⁺、Fe²⁺、Fe³⁺、Co²⁺And Co³⁺At least 1 kind of (1). The content of the metal ion Me1 is preferably 5 mol% or less, more preferably 2 mol% or less, and further preferably 0.1 mol% or less, based on 1 mol of the total metal ions of the metal azo pigment.

As for the metallic azo pigment, the description can be referred to paragraphs 0011 to 0062 and 0137 to 0276 of Japanese patent application laid-open No. 2017-171912, paragraphs 0010 to 0062 and 0138 to 0295 of Japanese patent application laid-open No. 2017-171913, paragraphs 0011 to 0062 and 0139 to 0190 of Japanese patent application laid-open No. 2017-171914, paragraphs 0010 to 0065 and 0142 to 0222 of Japanese patent application laid-open No. 2017-171915, and these contents are applied to the present description.

As the red pigment, a compound having a structure in which an aromatic ring group having an oxygen atom, a sulfur atom, or a nitrogen atom-bonded group introduced into an aromatic ring is bonded to a diketopyrrolopyrrole skeleton can be used. Such a compound is preferably a compound represented by the formula (DPP1), and more preferably a compound represented by the formula (DPP 2).

[ chemical formula 3]

In the above formula, R¹¹And R¹³Each independently represents a substituent, R¹²And R14 each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, n¹¹And n¹³Each independently represents an integer of 0 to 4, X¹²And X¹⁴Each independently represents an oxygen atom, a sulfur atom or a nitrogen atom, X¹²In the case of oxygen atom or sulfur atom, m¹²Represents 1, X¹²In the case of a nitrogen atom, m¹²Represents 2, X¹⁴In the case of oxygen atom or sulfur atom, m¹⁴Represents 1, X¹⁴In the case of a nitrogen atom, m¹⁴And 2. As R¹¹And R¹³The substituent represented by the formula (I) includes an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an amido group, a cyano group, a nitro group, a trifluoromethyl group, a sulfoxide group, a sulfo group and the like.

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 in1 molecule can be used. Specific examples thereof include compounds described in International publication WO 2015/118720.

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.

The dye is not particularly limited, and a known dye can be used. Examples thereof include dyes of pyrazolidine, phenylaminoazo, triarylmethane, anthraquinone, anthrapyridoquinone, benzylidene, oxonol, pyrazolotriazole, pyridone, cyanine, phenothiazine, pyrrolopyrazolomethylidene, xanthene, phthalocyanine, benzopyran, indigo, and pyrromethene. Also, multimers of these dyes may be used. Further, dyes described in Japanese patent laid-open Nos. 2015-028144 and 2015-034966 may be used.

(Black colorant)

Examples of the black coloring agent include inorganic black coloring agents such as carbon black, metal oxynitride (titanium black and the like), metal nitride (titanium nitride and the like), and organic black coloring agents such as dibenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds. The organic black colorant is preferably a dibenzofuranone compound or a perylene compound. Examples of the dibenzofuranone compound include those described in Japanese Kokai publication No. 2010-534726, Japanese Kokai publication No. 2012-515233, and Japanese Kokai publication No. 2012-515234, and can be obtained as "Irgaphor Black" manufactured by BASF corporation, for example. Examples of the perylene compound include c.i. Pigment Black (Pigment Black)31 and 32. Examples of the methine azo compound include those described in Japanese patent application laid-open Nos. H1-170601 and H2-34664, and can be obtained, for example, as "CHROMO FINE BLACK A1103" manufactured by Dainiciseika Color & Chemicals Mfg. Co., Ltd. The dibenzofuranone compound is preferably a compound represented by any one of the following formulae or a mixture thereof.

[ chemical formula 4]

In the formula, R¹And R²Each independently represents a hydrogen atom or a substituent, R³And R⁴Independently represents a substituent, a and b independently represent an integer of 0 to 4, and when a is 2 or more, a plurality of R³A plurality of R's, which may be the same or different, are³Can be bonded to form a ring, and when b is 2 or more, a plurality of R⁴A plurality of R's, which may be the same or different, are⁴May be bonded to form a ring.

R¹～R⁴The substituents are halogen atoms, cyano groups, nitro groups, alkyl groups, alkenyl groups, alkynyl groups, aralkyl groups, aryl groups, heteroaryl groups, -OR³⁰¹、-COR³⁰²、-COOR³⁰³、-OCOR³⁰⁴、-NR³⁰⁵R³⁰⁶、-NHCOR³⁰⁷、-CONR³⁰⁸R³⁰⁹、-NHCONR³¹⁰R³¹¹、-NHCOOR³¹²、-SR³¹³、-SO₂R³¹⁴、-SO₂OR³¹⁵、-NHSO₂R³¹⁶or-SO₂NR³¹⁷R³¹⁸，R³⁰¹～R³¹⁸Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.

The details of the dibenzofuranone compound can be found in paragraphs 0014 to 0037 of Japanese patent application publication No. 2010-534726, which are incorporated herein by reference.

(Infrared-absorbing dye)

The infrared absorbing dye is preferably the following compound. Namely, the absorption maximum wavelength is in the wavelength range of 700 to 1300nm, more preferably in the wavelength range of 700 to 1000 nm. The infrared absorbing pigment may be a pigment or a dye.

In the present invention, as the infrared absorbing dye, a compound having a pi-conjugated plane containing a monocyclic or condensed ring aromatic ring can be preferably used. The number of atoms other than hydrogen constituting the pi-conjugated plane of the infrared absorbing dye is preferably 14 or more, more preferably 20 or more, still more preferably 25 or more, and particularly preferably 30 or more. The upper limit is, for example, preferably 80 or less, more preferably 50 or less. The pi conjugated plane of the infrared absorbing dye preferably contains 2 or more monocyclic or condensed aromatic rings, more preferably 3 or more aromatic rings, still more preferably 4 or more aromatic rings, and particularly preferably 5 or more aromatic rings. The upper limit is preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less. Examples of the aromatic ring include a benzene ring, a naphthalene ring, a pentalene (pentalene) ring, an indene ring, an azulene ring, and a heptalene (heptalene)ne) ring, indene (indecene) ring, perylene ring, condensed pentacene ring, quarterylene (quaterrylene) ring, acenaphthene (acenaphtene) ring, phenanthrene ring, anthracene ring, condensed tetraphene (naphthacene) ring, perylene ring,

(chrysene) ring, terphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzoxazole ring, imidazoline ring, pyrazine (pyrazine) ring, quinoxaline (quinoline) ring, pyrimidine ring, quinazoline (quinazoline) ring, pyridazine (pyridazine) ring, triazine (triazine) ring, pyrrole ring, indole ring, isoindole ring, carbazole ring and condensed rings having these rings.

The infrared absorbing coloring matter is preferably at least one selected from the group consisting of a pyrrolopyrrole compound, a cyanine compound, a squaraine compound, a phthalocyanine compound, a naphthalocyanine compound, a quaterrylene compound, a merocyanine compound, a crotonium compound, an Oxonol compound, a diimine compound, a dithiol compound, a triarylmethane compound, a pyrromethene compound, a methine compound, an anthraquinone compound and a dibenzofuranone compound, more preferably at least one selected from the group consisting of a pyrrolopyrrole compound, a cyanine compound, a squaraine compound, a phthalocyanine compound, a naphthalocyanine compound and a bisimine compound, further preferably at least one selected from the group consisting of a pyrrolopyrrole compound, a cyanine compound and a squaraine compound, and particularly preferably a pyrrolopyrrole compound.

Examples of the pyrrolopyrrole compound include compounds described in paragraphs 0016 to 0058 of Japanese patent laid-open No. 2009-263614, compounds described in paragraphs 0037 to 0052 of Japanese patent laid-open No. 2011-68731, and compounds described in paragraphs 0010 to 0033 of International publication WO2015/166873, and the contents of these are incorporated in the present specification.

Examples of the squarylium compound include compounds described in paragraphs 0044 to 0049 of Japanese patent application laid-open No. 2011-208101, compounds described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 6065169, compounds described in paragraph 0040 of International publication No. WO2016/181987, compounds described in International publication No. WO2013/133099, compounds described in International publication No. WO2014/088063, compounds described in Japanese patent application laid-open No. 2014-126642, compounds described in Japanese patent application laid-open No. 2016-146619, compounds described in Japanese patent application laid-open No. 2015-176046, compounds described in Japanese patent application laid-open No. 2017-25311, compounds described in International patent application laid-open No. WO2016/154782, compounds described in Japanese patent application laid-open No. 5884953, compounds described in Japanese patent laid-open No. 6036689, compounds described in Japanese patent laid-open No. 2011-open No. 0044 to 0049, compounds described in Japanese patent application laid-open No. 6065169, The compounds described in Japanese patent No. 5810604, and the compounds described in Japanese patent application laid-open No. 2017-068120, are incorporated in the present specification.

Examples of the cyanine compound include compounds described in paragraphs 0044 to 0045 of Japanese patent application laid-open No. 2009-108267, compounds described in paragraphs 0026 to 0030 of Japanese patent application laid-open No. 2002-194040, compounds described in Japanese patent application laid-open No. 2015-172004, compounds described in Japanese patent application laid-open No. 2015-172102, compounds described in Japanese patent application laid-open No. 2008-088426, and compounds described in Japanese patent application laid-open No. 2017-031394, and these are incorporated herein by reference.

Examples of the diimine compound include those described in JP-A-2008-528706, the contents of which are incorporated herein by reference. Examples of the phthalocyanine compound include compounds described in paragraph 0093 of Japanese patent laid-open No. 2012 and 077153, titanyl phthalocyanine described in Japanese patent laid-open No. 2006 and 343631, and compounds described in paragraphs 0013 to 0029 of Japanese patent laid-open No. 2013 and 195480, and these are incorporated herein by reference. Examples of the naphthalocyanine compound include compounds described in paragraph 0093 of Japanese patent application laid-open No. 2012-077153, the contents of which are incorporated in the present specification.

In the present invention, commercially available infrared absorbing dyes can also be used. Examples thereof include SDO-C33 (manufactured by Arimoto Chemical Co. Ltd.), EX Color IR-14, EX Color IR-10A, EX Color TX-EX-801B, EXcolor TX-EX-805K (manufactured by Nippon Shokubai Co., Ltd.), Shigenox NIA-8041, Shigenox NIA-8042, Shigenox NIA-814, Shigenox NIA-820, Shigenox NIA-839 (manufactured by HAKKO Chemical Co., Ltd.), Epolite V-63, Eplight 3801, Eplight 3036 (manufactured by LIN Co., Ltd.), PRO-JET 825I (manufactured by LDFUJIFILM Co., Ltd.), NK-3027, NK-5060 (manufactured by Hayashi Co., Ltd.), Ltd.), Ytsui-KR 70 (manufactured by Mitsui Chemical Co., Ltd.), and the like.

From the viewpoint of making the film obtained thinner, the content of the color material in the total solid content of the photosensitive composition is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more. When the content of the color material is 40% by mass or more, a thin film can be easily formed and a film having good spectral characteristics can be easily formed. From the viewpoint of film-forming properties, 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.

The coloring material used in the photosensitive composition of the present invention preferably contains at least one selected from a color coloring agent and a black coloring agent. The content of the color colorant and the black colorant in the total mass of the coloring material is preferably 30 mass% or more, more preferably 50 mass% or more, and still more preferably 70 mass% or more. The upper limit may be set to 100 mass% or less, and may be set to 90 mass% or less.

The coloring material used in the photosensitive composition of the present invention preferably contains at least a green coloring agent. The content of the green colorant in the total mass of the coloring material is preferably 30 mass% or more, more preferably 40 mass% or more, and still more preferably 50 mass% or more. The upper limit may be set to 100 mass% or less, and may be set to 75 mass% or less.

The content of the pigment in the coloring material used in the photosensitive composition of the present invention is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, based on the total mass of the coloring material. When the content of the pigment in the total mass of the color material is within the above range, a film in which spectral variation due to heat is suppressed can be easily obtained.

When the photosensitive composition of the present invention is used as a composition for forming a colored pixel, the content of the color colorant in the total solid content of the photosensitive composition is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more. The content of the color colorant in the total mass of the coloring material is preferably 25 mass% or more, more preferably 45 mass% or more, and still more preferably 65 mass% or more. The upper limit may be set to 100 mass% or less, and may be set to 75 mass% or less. The coloring material preferably contains at least a green coloring agent. The content of the green colorant in the total mass of the coloring material is preferably 35 mass% or more, more preferably 45 mass% or more, and still more preferably 55 mass% or more. The upper limit may be 100 mass% or less, and may be 80 mass% or less.

When the photosensitive composition of the present invention is used as a composition for forming a black pixel or a shielding film, the content of the black colorant (preferably, an inorganic black colorant) in the total solid content of the photosensitive composition is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, and particularly preferably 60% by mass or more. The content of the black colorant in the total mass of the coloring material is preferably 30 mass% or more, more preferably 50 mass% or more, and still more preferably 70 mass% or more. The upper limit may be set to 100 mass% or less, and may be set to 90 mass% or less.

When the photosensitive composition of the present invention is used as a composition for forming a pixel of an infrared-transmitting filter layer, the coloring material used in the present invention preferably satisfies at least one of the following requirements (1) to (3).

(1): two or more color colorants are contained and black is formed in a combination of two or more color colorants. It is preferable that the black color is formed by a combination of two or more colorants selected from a red colorant, a blue colorant, a yellow colorant, a violet colorant, and a green colorant.

(2): comprising an organic black colorant.

(3): the above (1) or (2) further contains an infrared absorbing dye.

Preferable combinations of the above-mentioned modes (1) include, for example, the following.

(1-1) embodiment containing a red colorant and a blue colorant.

(1-2) embodiment containing a red colorant, a blue colorant and a yellow colorant.

(1-3) the embodiment containing a red colorant, a blue colorant, a yellow colorant and a violet colorant.

(1-4) the embodiment containing a red colorant, a blue colorant, a yellow colorant, a violet colorant and a green colorant.

(1-5) embodiment containing a red colorant, a blue colorant, a yellow colorant and a green colorant.

(1-6) embodiment containing a red colorant, a blue colorant and a green colorant.

(1-7) embodiment containing a yellow colorant and a violet colorant.

In the embodiment (2), it is preferable that the ink further contains a color colorant. By using the organic black coloring agent and the color coloring agent in combination, excellent spectral characteristics can be easily obtained. Examples of the color colorant used in combination with the organic black colorant include a red colorant, a blue colorant, and a violet colorant, and the red colorant and the blue colorant are preferable. These may be used alone or in combination of two or more. The mixing ratio of the color colorant and the organic black colorant is preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass, based on 100 parts by mass of the organic black colorant.

In the embodiment (3), the content of the infrared absorbing coloring matter in the total mass of the coloring material is preferably 5 to 40% by mass. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.

Photoinitiator B

The photosensitive composition of the present invention contains a photoinitiator B. Examples of the photoinitiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and they can be selected and used according to the kind of the compound C described later. When a radical polymerizable compound is used as the compound C, a photo radical polymerization initiator is preferably used as the photoinitiator B. When a cationically polymerizable compound is used as the compound C, a photocationic polymerization initiator is preferably used as the photoinitiator B.

The photoinitiator B preferably contains at least 1 compound selected from the group consisting of an alkylphenone compound, an acylphosphine compound, a benzophenone compound, a thioxanthone compound, a triazine compound, and an oxime compound, and more preferably contains an oxime compound.

Examples of the alkylphenone compound include benzyl dimethyl ketal compounds, α -hydroxyalkylphenone compounds, α -aminoalkylphenone compounds, and the like.

Examples of the benzyldimethyl ketal compound include 2, 2-dimethoxy-2-phenylacetophenone and the like. Examples of commercially available products include IRGACURE-651 (manufactured by BASF corporation).

Examples of the α -hydroxyalkylphenone compounds include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one. Commercially available products of the α -hydroxyalkylphenone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (manufactured by BASF).

Examples of the α -aminoalkylphenone compound include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and 2-dimethylamino-2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone. Commercially available products of the α -aminoalkylphenone compounds include IRGACURE-907, IRGACURE-369, and IRGACURE-379 (manufactured by BASF corporation).

Examples of the acylphosphine compound include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, and the like. As commercially available acylphosphine compounds, IRGACURE-819 and IRGACURE-TPO (manufactured by BASF) can be mentioned.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3',4,4' -tetrakis (t-butylperoxyhydroxy) benzophenone, and 2,4, 6-trimethylbenzophenone.

Examples of the thioxanthone compound include 2-isopropyl-thioxanthone, 4-isopropyl-thioxanthone, 2, 4-diethyl-thioxanthone, 2, 4-dichloro-thioxanthone, and 1-chloro-4-propoxy-thioxanthone.

Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl ] -1,3, 5-triazine 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine, and the like.

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. 201019766, and a compound described in Japanese patent laid-open No. 6065596, A compound described in International publication WO2015/152153, a compound described in International publication WO2017/051680, or the like. 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 oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (manufactured by BASF Co., Ltd.), TR-PBG-304 (manufactured by CHANGZHHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), and ADECAOPTOMER N-1919 (photopolymerization initiator 2 disclosed in Japanese patent application laid-open No. 2012-014052, manufactured by ADEKA CORPORATION). Further, as the oxime compound, a compound having no coloring property and high transparency and hardly discoloring other components is preferably used. Examples of commercially available products include ADEKA ARKLS NCI-730, NCI-831 and NCI-930 (manufactured by ADEKACORPORATION).

In the present invention, as the photoinitiator B, 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. This content is used in the present description.

In the present invention, as the photoinitiator B, 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. This content is used in the present description.

In the present invention, as the photoinitiator B, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably provided as 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, paragraphs 0008 to 0012 and paragraphs 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 ADEKA ARKLSNCI-831 (manufactured by ADEKA CORPORATION).

In the present invention, as the photoinitiator B, an oxime compound having a benzofuran skeleton can also be used. Specific examples thereof include OE-01 to OE-75 disclosed in International publication WO 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 5]

[ chemical formula 6]

In the present invention, as the photoinitiator B, a 2-functional or 3-functional photoradical polymerization initiator can be used. By using these photo radical polymerization initiators, 2 or more radicals are generated from 1 molecule of the photo radical polymerization initiator, and thus a 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 difficult, whereby the stability with time of the photosensitive composition can be improved. Specific examples of the 2-or 3-or more-functional photo radical polymerization initiator include dimers of oxime compounds described in JP-A2010-527339, JP-A2011-524436, International publication WO2015/004565, paragraphs 0412 to 0417 in JP-A2016-532675, paragraphs 0039 to 0055 in International publication WO2017/033680, the compound (E) and the compound (G) described in JP-A-2013-522445, Cmpd 1-7 described in WO2016/034963, the oxime ester photoinitiator described in paragraph 0007 of JP-A-2017-523465, the photoinitiator described in paragraphs 0020-0033 of JP-A-2017-167399, the photopolymerization initiator (A) described in paragraphs 0017-0026 of JP-A-2017-151342, and the like.

In the present invention, a pinacol compound can also be used as the photoinitiator B. Examples of the pinacol compound include benzopinacol, 1, 2-dimethoxy-1, 1,2, 2-tetraphenylethane, 1, 2-diethoxy-1, 1,2, 2-tetraphenylethane, 1, 2-diphenoxy-1, 1,2, 2-tetraphenylethane, 1, 2-dimethoxy-1, 1,2, 2-tetrakis (4-methylphenyl) ethane, 1, 2-diphenoxy-1, 1,2, 2-tetrakis (4-methoxyphenyl) ethane, 1, 2-bis (trimethylsiloxy) -1,1,2, 2-tetraphenylethane, 1, 2-bis (triethylsilanoxy) -1,1,2, 2-tetraphenylethane, 1, 2-bis (tert-butyldimethylsiloxy) -1,1,2, 2-tetraphenylethane, 1-hydroxy-2-trimethylsilyloxy-1, 1,2, 2-tetraphenylethane, 1-hydroxy-2-triethylsilanyloxy-1, 1,2, 2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethylsilyloxy-1, 1,2, 2-tetraphenylethane and the like. Further, as to the pinacol compound, reference can be made to the descriptions of Japanese patent application publication Nos. 2014-521772, 2014-523939 and 2014-521772, and these contents are incorporated in the present description.

In the present invention, as the photoinitiator B, a photoinitiator B1 containing a photoinitiator satisfying the following condition 1 was used.

Condition 1: at the maximum instant of the illuminance 375000000W/m²The quantum yield q after pulse exposure of a propylene glycol monomethyl ether acetate solution containing 0.035mmol/L of photoinitiator b1 to light having a wavelength of 355nm under conditions of a pulse width of 8 ns and a frequency of 10Hz₃₅₅Is 0.05 or more.

Quantum yield q of photoinitiator b1₃₅₅Preferably 0.10 or more, more preferably 0.15 or more, more preferably 0.25 or more, still more preferably 0.35 or more, and particularly preferably 0.45 or more. Further, the active species generated from the photoinitiator B by the exposure under the above condition 1 is preferably a radical.

In this specification, the quantum yield q of photoinitiator b1₃₅₅The number of decomposed molecules of the photoinitiator b1 after pulse exposure under the condition 1 was divided by the number of absorbed photons of the photoinitiator b 1.The number of absorbed photons is determined from the time of exposure by pulse exposure under the above condition 1, the absorbance at 355nm before and after exposure is converted into the transmittance, and the number of absorbed photons is multiplied by (1-transmittance), thereby determining the number of absorbed photons the number of decomposed molecules is determined from the absorbance of the photoinitiator b1 after exposure, the decomposition rate of the photoinitiator b1 is determined from the absorbance of the photoinitiator b1, and the number of existing molecules of the photoinitiator b1 is multiplied by the decomposition rate, and the number of decomposed molecules is determined by adding a propylene glycol monomethyl ether acetate solution containing 0.035mmol/L of the photoinitiator b1 to an optical cell (opticalcelll) of 1cm × cm × cm, so that the absorbance of the initiator b1 can be measured using a spectrophotometer, for example, hp8453 manufactured by Agilent corporation can be used as the photoinitiator b1 satisfying the above condition 1, IRGACURE-OXE01, OXE02, OXE 4 (the above conditions are satisfied), and the compound can be preferably used as the photoinitiator b 01, and the above mentioned irgaxre 01 can be used from the viewpoint of the structural properties.

[ chemical formula 7]

Further, the photoinitiator b1 preferably satisfies the following condition 2.

Condition 2: at the maximum instant of the illuminance 375000000W/m²The quantum yield q after pulse exposure of light having a wavelength of 265nm to a film having a thickness of 1.0 μm and containing 5% by mass of photoinitiator b1 and 95% by mass of resin under conditions of a pulse width of 8 ns and a frequency of 10Hz₂₆₅Is 0.05 or more.

Quantum yield q of photoinitiator b1₂₆₅Preferably 0.10 or more, more preferably 0.15 or more, and further preferably 0.20 or more.

In this specification, the quantum yield q of photoinitiator b1₂₆₅Is every 1cm after pulse exposure under the condition of the above-mentioned condition 2²The number of decomposed molecules of the photoinitiator b1 of the film was divided by the number of absorbed photons of the photoinitiator b 1. With respect to the number of absorbed photons, fromThe number of photons irradiated was determined for the exposure time by pulse exposure under the condition of the above-mentioned condition 2, and the number of photons irradiated per 1cm²The number of photons absorbed was determined by multiplying the number of photons irradiated to the film by (1-transmittance). The decomposition rate of the photoinitiator b1 was determined from the change in absorbance of the film before and after exposure, and the decomposition rate of the photoinitiator b1 was multiplied by the value of 1cm per unit²The number of existing molecules of the photoinitiator b1 in the film was determined for each 1cm after exposure²Number of decomposed molecules of the photoinitiator b1 of the film. The film density was defined as 1.2g/cm³Determining the area of each membrane to be 1cm²As "((per 1 cm))²The film weight was × 5 mass% (content of initiator b 1)/molecular weight of initiator b1) × 6.02.02 6.02 × 1023 (Avoganlo constant)) "and the film weight was determined for each 1cm²The number of existing molecules of the photoinitiator b1 in the film.

The photoinitiator b1 used in the present invention preferably satisfies the following condition 3.

Condition 3: at the maximum instant of the illuminance 625000000W/m²A film containing 5% by mass of photoinitiator b1 and a resin was exposed to light having a wavelength of 248 to 365nm at 1 pulse under conditions of a pulse width of 8 ns and a frequency of 10Hz, and the exposure was carried out every 1cm²The concentration of active species in the membrane of the membrane reaches more than 0.000000001 mmol.

The concentration of active species in the above-mentioned membrane in the above-mentioned condition 3 is preferably up to 1cm per unit²The film is 0.000000005mmol or more, more preferably 0.00000001mmol or more, still more preferably 0.00000003mmol or more, particularly preferably 0.0000001mmol or more.

In addition, in the present specification, the decomposition rate per the number of incident photons was calculated by multiplying the quantum yield of the initiator b1 in the measured wavelength of light by (1-transmittance of film), and the decomposition rate per 1cm per the number of incident photons was calculated from "the number of moles of photons per 1 pulse" × "and the decomposition rate of the initiator b1 per the number of incident photons" in the present specification²The concentration of the active species in the above-mentioned film was determined from the concentration of the initiator b1 for film decomposition. In addition, when the active species concentration is calculated, the value is calculated assuming that the initiator b1 decomposed by light irradiation becomes all active species (does not disappear after the reaction in the middle).

The resin used for the measurement in the above conditions 2 and 3 is not particularly limited as long as it has compatibility with the photoinitiator b 1. For example, the resin (A) having the following structure can be preferably used. The values appended to the repeating units are molar ratios, a weight average molecular weight of 40000 and a dispersity (Mn/Mw) of 5.0.

Resin (A)

[ chemical formula 8]

The photoinitiator b1 is preferably an alkylbenzene ketone compound or an oxime compound, and more preferably an oxime compound, because the concentration of the active species generated is high. Also, the photoinitiator b1 is preferably one which readily absorbs two photons. In addition, two-photon absorption refers to an excitation process that absorbs two photons simultaneously.

The photoinitiator B used in the present invention may contain only 1 kind, or may contain 2 or more kinds of photoinitiators. When the photoinitiator B contains 2 or more photoinitiators, each initiator may be the photoinitiator B1 satisfying the above condition 1. Further, 1 or more kinds of the photoinitiator b1 satisfying the above condition 1 and the photoinitiator b2 not satisfying the above condition 1 may be contained. From the viewpoint of easily generating a required amount of active species, the 2 or more kinds of initiators included in the photoinitiator B are preferably only the photoinitiator B1 satisfying the above condition 1. Further, from the viewpoint of the reason that the desensitization with time is easily suppressed, it is preferable that the 2 or more photoinitiators contained in the photoinitiator B contain 1 or more photoinitiators B1 satisfying the above condition 1 and photoinitiators B2 not satisfying the above condition 1, respectively. Examples of the photoinitiator b2 which does not satisfy the above condition 1 include pinacol compounds such as benzopinacol.

The photoinitiator B used in the present invention preferably contains 2 or more photoinitiators for the reason of easy adjustment of sensitivity.

From the viewpoint of curability, the photoinitiator B used in the present invention preferably satisfies the following condition 1 a.

Condition1 a: at the maximum instant of the illuminance 375000000W/m²The quantum yield q after pulse exposure of a propylene glycol monomethyl ether acetate solution containing 0.035mmol/L of a mixture containing 2 or more photoinitiators in a proportion contained in the photosensitive composition to light having a wavelength of 355nm under conditions of a pulse width of 8 ns and a frequency of 10Hz₃₅₅Preferably 0.05 or more, more preferably 0.10 or more, more preferably 0.15 or more, still more preferably 0.25 or more, still more preferably 0.35 or more, and particularly preferably 0.45 or more.

From the viewpoint of curability, the photoinitiator B used in the present invention preferably satisfies the following condition 2 a.

Condition 2 a: at the maximum instant of the illuminance 375000000W/m²A quantum yield q after pulse exposure of light having a wavelength of 265nm to a film having a thickness of 1.0 μm and containing 5% by mass of a mixture containing 2 or more photoinitiators and 95% by mass of a resin in a proportion contained in a photosensitive composition under conditions of a pulse width of 8 ns and a frequency of 10Hz₂₆₅Preferably 0.05 or more, more preferably 0.10 or more, more preferably 0.15 or more, and particularly preferably 0.20 or more.

From the viewpoint of curability, the photoinitiator B used in the present invention preferably satisfies the following condition 3 a.

Condition 3 a: at the maximum instant of the illuminance 625000000W/m²Preferably, the concentration of active species in a film containing 5% by mass of a resin and a mixture of 2 or more photoinitiators in a proportion contained in the photosensitive composition is such that the concentration of active species in the film per 1cm after pulse exposure for 0.1 second to light having a wavelength within the range of 248 to 365nm under conditions of a pulse width of 8 ns and a frequency of 10Hz²The film is 0.000000001mmol or more, more preferably 0.000000005mmol or more, still more preferably 0.00000001mmol or more, particularly preferably 0.00000003mmol or more, and most preferably 0.0000001mmol or more.

The content of the photoinitiator B in the total solid content of the photosensitive composition is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 7% by mass or less, from the viewpoint of the ease of suppressing the pattern thickness. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more. From the viewpoint of curability, the content of the photoinitiator B is preferably 10 to 200 parts by mass with respect to 100 parts by mass of the compound C described later. The upper limit is preferably 100 parts by mass or less, and more preferably 50 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. When the photosensitive composition of the present invention contains 2 or more types of photoinitiators B, the total amount of these is preferably within the above range.

The content of the photoinitiator b1 in the total solid content of the photosensitive composition is preferably 15 mass% or less, more preferably 10 mass% or less, and still more preferably 7 mass% or less, for the reason that the pattern thickness can be easily suppressed. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more. From the viewpoint of curability, the content of the photoinitiator b1 is preferably 10 to 200 parts by mass per 100 parts by mass of the compound C described later. The upper limit is preferably 100 parts by mass or less, and more preferably 50 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. When the photosensitive composition of the present invention contains 2 or more kinds of photoinitiators b1, the total amount of these photoinitiators is preferably within the above range.

Compound C

The photosensitive composition of the present invention contains a compound C which is cured by reaction of active species generated from a photoinitiator B. Examples of the compound C include polymerizable compounds such as radical polymerizable compounds and cation polymerizable compounds. Examples of the radical polymerizable compound include compounds having an ethylenically unsaturated bond group such as a vinyl group, (meth) allyl group, or (meth) acryloyl group. Examples of the cationically polymerizable compound include compounds having a cyclic ether group such as an epoxy group or an oxetane group.

The compound C may be a monomer (hereinafter also referred to as a polymerizable monomer) or a polymer (hereinafter also referred to as a polymerizable polymer). The molecular weight of the polymerizable monomer is preferably less than 2000, more preferably 1500 or less, and further preferably 1000 or less. The lower limit is preferably 100 or more, and more preferably 150 or more. The weight average molecular weight (Mw) of the polymerizable polymer 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, and more preferably 5000 or more. The polymerizable polymer can also be used as a resin described later.

In the present invention, as the compound C, a polymerizable monomer and a polymerizable polymer may be used in combination. By using both, the coating property and the curability can be easily achieved. When both are used in combination, the content of the polymerizable monomer is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, and still more preferably 50 to 200 parts by mass, per 100 parts by mass of the polymerizable polymer.

In the present invention, the compound C is preferably a radical polymerizable compound, and more preferably a radical polymerizable monomer. By subjecting the radical polymerizable compound to pulse exposure, radicals can be generated from the radical polymerizable compound, and the radical polymerizable compound can be cured more efficiently, whereby a photosensitive composition having excellent curability can be obtained. In particular, in the case of a radically polymerizable monomer, it is possible to more efficiently generate radicals and to more efficiently cure the radically polymerizable monomer.

(polymerizable monomer)

The polymerizable monomer is preferably a 2-or more-functional polymerizable monomer, more preferably a 2-to 15-functional polymerizable monomer, still more preferably a 2-to 10-functional polymerizable monomer, and particularly preferably a 2-to 6-functional polymerizable monomer.

In the present invention, it is also preferable to use a polymerizable monomer having a fluorene skeleton as the polymerizable monomer. It is considered that, even if a large amount of active species such as radicals are instantaneously generated from the photoinitiator B by pulse exposure, it is difficult to generate a self-reaction such as a reaction of polymerizable groups with each other in the same molecule, and a film having a high crosslinking density or the like can be formed by efficiently curing the polymerizable monomer by pulse exposure.

Examples of the polymerizable monomer having a fluorene skeleton include compounds having a partial structure represented by the following formula (Fr).

(Fr)

[ chemical formula 9]

Wherein the wavy line represents a bond, R^f1And R^f2Each independently represents a substituent, and m and n each independently represent an integer of 0 to 5. When m is 2 or more, m R^f1M R's may be the same or different^f12 of R^f1The ring may be bonded to each other to form a ring. When n is 2 or more, n R^f2N R's may be the same or different^f22 of R^f2The ring may be bonded to each other to form a ring. As R^f1And R^f2Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heteroaryl group and-OR^f11、-COR^f12、-COOR^f13、-OCOR^f14、-NR^f15R^f16、-NHCOR^f17、-CONR^f18R^f19、-NHCONR^f20R^f21、-NHCOOR^f22、-SR^f23、-SO₂R^f24、-SO₂OR^f25、-NHSO₂R^f26or-SO₂NR^f27R^f28。R^f11～R^f28Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.

The polymerizable group value of the polymerizable monomer is preferably 2mmol/g or more, more preferably 6mmol/g or more, and still more preferably 10mmol/g or more. The upper limit is preferably 30mmol/g or less. When the polymerizable group value of the polymerizable monomer is 2mmol/g or more, the curing property of the photosensitive composition is good. The polymerizable group value of the polymerizable monomer is calculated by dividing the number of polymerizable groups contained in1 molecule of the polymerizable monomer by the molecular weight of the polymerizable monomer.

[ radically polymerizable monomer ]

The radical polymerizable monomer is preferably a compound having 2 or more ethylenically unsaturated bond groups (compound having 2 or more functional groups), more preferably a compound having 2 to 15 ethylenically unsaturated bond groups (compound having 2 to 15 functional groups), more preferably a compound having 2 to 10 ethylenically unsaturated bond groups (compound having 2 to 10 functional groups), and particularly preferably a compound having 2 to 6 ethylenically unsaturated bond groups (compound having 2 to 6 functional groups). Specifically, the radical polymerizable monomer is preferably a 2-or more-functional (meth) acrylate compound, more preferably a 2-15-functional (meth) acrylate compound, still more preferably a 2-10-functional (meth) acrylate compound, and particularly preferably a 2-6-functional (meth) acrylate compound. Specific examples thereof include the compounds described in paragraphs 0095 to 0108 of Japanese patent application laid-open No. 2009 and 288705, 0227 of Japanese patent application laid-open No. 2013 and 029760, and 0254 to 0257 of Japanese patent application laid-open No. 2008 and 29292970, which are incorporated herein by reference.

The value of the ethylenically unsaturated bond group of the radical polymerizable monomer (hereinafter referred to as "C ═ C value") is preferably 2mmol/g or more, more preferably 6mmol/g or more, and further preferably 10mol/g or more for the reason of improving curability. The upper limit is preferably 30mmol/g or less. The C ═ C value of the radical polymerizable monomer was calculated by dividing the number of ethylenically unsaturated bond groups contained in1 molecule of the radical polymerizable monomer by the molecular weight of the polymerizable monomer.

The radical polymerizable monomer is preferably a radical polymerizable monomer having a fluorene skeleton, and more preferably a radical polymerizable monomer having a partial structure represented by the above formula (Fr). The radical polymerizable monomer having a fluorene skeleton is preferably a compound having 2 or more ethylenically unsaturated bond groups, more preferably a compound having 2 to 15 ethylenically unsaturated bond groups, still more preferably a compound having 2 to 10 ethylenically unsaturated bond groups, and particularly preferably a compound having 2 to 6 ethylenically unsaturated bond groups. Specific examples of the radical polymerizable monomer having a fluorene skeleton include compounds having the following structures. Commercially available products of radical polymerizable monomers 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.).

[ chemical formula 10]

The radical polymerizable monomer can also preferably use compounds represented by the following formulas (MO-1) to (MO-6). In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

[ chemical formula 11]

In the above formula, n is 0 to 14, and m is 1 to 8. The plurality of R, T present in a molecule may be the same or different.

In the compounds represented by the above formulae (MO-1) to (MO-6), at least 1 of the plurality of R represents-OC (═ O) CH ═ CH₂、-OC(＝O)C(CH₃)＝CH₂、-NHC(＝O)CH＝CH₂or-NHC (═ O) C (CH)₃)＝CH₂。

Specific examples of the polymerizable compounds represented by the above formulas (MO-1) to (MO-6) include the compounds described in paragraphs 0248 to 0251 of Japanese patent application laid-open No. 2007-269779.

The radical polymerizable monomer is preferably a compound having a caprolactone structure. The compound having a caprolactone structure is preferably a compound represented by the following formula (Z-1).

[ chemical formula 12]

In the formula (Z-1), 6 Rs are each a group represented by the formula (Z-2) or 1 to 5 of the 6 Rs are groups represented by the formula (Z-2), and the remainder is a group represented by the formula (Z-3), an acid group or a hydroxyl group.

[ chemical formula 13]

In the formula (Z-2), R¹Represents hydrogenAn atom or a methyl group, m represents a number of 1 or 2, and "" represents a bond.

[ chemical formula 14]

In the formula (Z-3), R¹Represents a hydrogen atom or a methyl group, "-" represents a bonding bond.

As the radical polymerizable monomer, a compound represented by the formula (Z-4) or (Z-5) can also be used.

[ chemical formula 15]

In the formulae (Z-4) and (Z-5), E independently represents- ((CH)₂)_yCH₂O) -, or- ((CH₂)_yCH(CH₃) O) -, y independently represent an integer of 0 to 10, and X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group. In the formula (Z-4), the total number of (meth) acryloyl groups is 3 or 4, m independently represents an integer of 0 to 10, and the total number of m is an integer of 0 to 40. In the formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, n independently represents an integer of 0 to 10, and the total number of n is an integer of 0 to 60.

In the formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The total of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.

In the formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The total of n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

And- ((CH) in the formula (Z-4) or the formula (Z-5)₂)_yCH₂O) -, or- ((CH₂)_yCH(CH₃) O) -preferably a form in which the oxygen atom side terminal is bonded to X.

[ cationically polymerizable monomer ]

The cationically polymerizable monomer is preferably a compound having 2 or more cyclic ether groups (a compound having 2 or more functional groups), more preferably a compound having 2 to 15 cyclic ether groups (a compound having 2 to 15 functional groups), still more preferably a compound having 2 to 10 cyclic ether groups (a compound having 2 to 10 functional groups), and particularly preferably a compound having 2 to 6 cyclic ether groups (a compound having 2 to 6 functional groups). Specifically, compounds described in paragraphs 0034 to 0036 of Japanese patent application laid-open No. 2013 and 011869 and paragraphs 0085 to 0090 of Japanese patent application laid-open No. 2014 and 089408 can be used. These matters are used in the present description.

Examples of the cationically polymerizable monomer include compounds represented by the following formula (EP 1).

[ chemical formula 16]

In the formula (EP1), R^EP1～R^EP3Each represents a hydrogen atom, a halogen atom, or an alkyl group, and the alkyl group may have a cyclic structure or may have a substituent. And, R^EP1And R^EP2、R^EP2And R^EP3May be bonded to each other to form a ring structure. Q^EPRepresents a single bond or n^EPA monovalent organic group. R^EP1～R^EP3Can be reacted with Q^EPBonded to form a ring structure. n is^EPRepresents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6. Wherein Q is^EPIn the case of a single bond, n^EPIs 2. With respect to R^EP1～R^EP3、Q^EPReference is made to the description of paragraphs 0087 to 0088 of jp 2014-089408 a, which is incorporated herein by reference. Specific examples of the compound represented by the formula (EP1) include the compound described in paragraph 0090 of jp 2014-089408 a and the compound described in paragraph 0151 of jp 2010-054632 a, and these are incorporated in the present specification.

Commercially available products of the cationically polymerizable monomer include an ADEKA Glycerol series manufactured by ADEKA CORPORATION (for example, ADEKA Glycol ED-505), an EPOLEAD series manufactured by Daicel CORPORATION (for example, EPOLEAD GT 401), and the like.

(polymerizable Polymer)

Examples of the polymerizable polymer include a resin containing a repeating unit having a polymerizable group, an epoxy resin, and the like.

Examples of the repeating unit having a polymerizable group include the following (A2-1) to (A2-4).

[ chemical formula 17]

R¹Represents a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. R¹Preferably a hydrogen atom or a methyl group.

L⁵¹Represents a single bond or a 2-valent linking group. As the linking group having a valence of 2, there may be mentioned alkylene, arylene, -O-, -S-, -CO-, -COO-, -OCO-, -SO₂-、-NR¹⁰-(R¹⁰Represents a hydrogen atom or an alkyl group, preferably a hydrogen atom) or a group composed of these combinations. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 15, and still more preferably 1 to 10. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be any of linear, branched, and cyclic. The cyclic alkylene group may be either monocyclic or polycyclic. The number of carbon atoms of the arylene group is preferably 6 to 18, more preferably 6 to 14, and further preferably 6 to 10.

P¹Represents a polymerizable group. Examples of the polymerizable group include ethylenically unsaturated bond groups such as a vinyl group, (meth) allyl group, and (meth) acryloyl group; cyclic ether groups such as epoxy groups and oxetane groups.

Examples of the epoxy resin include epoxy resins which are glycidyl etherates of phenol compounds, epoxy resins which are glycidyl etherates of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins which are glycidyl groups of halogenated phenols, condensates of silicon compounds having epoxy groups with silicon compounds other than these, copolymers of polymerizable unsaturated compounds having epoxy groups with polymerizable unsaturated compounds other than these, and the like. The epoxy equivalent of the epoxy resin is preferably 310 to 3300g/eq, more preferably 310 to 1700g/eq, and further preferably 310 to 1000 g/eq. Examples of commercially available epoxy resins include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (which is a polymer containing an epoxy group manufactured by NOF CORPORATION). As the epoxy resin, the epoxy resins described in paragraphs 0153 to 0155 of Japanese patent application laid-open No. 2014-043556 and paragraphs 0092 of Japanese patent application laid-open No. 2014-089408 can be used, and these contents are referred to in the present description.

As the polymerizable polymer, a resin having a fluorene skeleton can also be used. Examples of the resin having a fluorene skeleton include resins having the following structures. In the following structural formula, A is a residue of carboxylic dianhydride selected from pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride and diphenyl ether tetracarboxylic dianhydride, and M is phenyl or benzyl. As for the resin having a fluorene skeleton, reference can be made to the description of U.S. patent application publication No. 2017/0102610, the contents of which are incorporated in the present description.

[ chemical formula 18]

The polymerizable group value of the polymerizable polymer is preferably 0.5 to 3 mmol/g. The upper limit is preferably 2.5mmol/g or less, more preferably 2mmol/g or less. The lower limit is preferably 0.9mmol/g or more, more preferably 1.2mmol/g or more. The polymerizable group value of the polymerizable polymer is a numerical value indicating a molar amount of the polymerizable group value per 1g of the solid content of the polymerizable polymer. The polymerizable polymer preferably has a C value of 0.6 to 2.8 mmol/g. The upper limit is preferably 2.3mmol/g or less, more preferably 1.8mmol/g or less. The lower limit is preferably 1.0mmol/g or more, more preferably 1.3mmol/g or more. The value of C ═ C of the polymerizable polymer is a numerical value indicating the molar amount of the ethylenically unsaturated bond group per 1g of the solid content of the polymerizable polymer.

The polymerizable polymer also preferably contains a repeating unit having an acid group. Such polymers can be used as alkali-soluble resins. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and a carboxyl group is preferable. When the polymerizable polymer contains a repeating unit having an acid group, the acid value of the polymerizable polymer is preferably 30 to 200 mgKOH/g. The lower limit is preferably 50mgKOH/g or more, more preferably 70mgKOH/g or more, and still more preferably 100mgKOH/g or more. The upper limit is preferably not more than 180mgKOH/g, more preferably not more than 150 mgKOH/g.

Specific examples of the polymerizable polymer include resins having the following structures.

[ chemical formula 19]

The content of the compound C in the total solid content of the photosensitive composition is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less, from the viewpoint of the ease of suppressing the thickness of the pattern. From the viewpoint of curability, the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 8% by mass or more.

The content of the polymerizable monomer in the total solid content of the photosensitive composition is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less, from the viewpoint of the ease of suppressing the thickness of the pattern. From the viewpoint of curability, the lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more.

The content of the polymerizable polymer in the total solid content of the photosensitive composition is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less, from the viewpoint of the ease of suppressing the thickness of the pattern. From the viewpoint of curability, the lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more.

Resin (resin)

The photosensitive composition of the present invention may contain a resin. In the present invention, the resin is an organic compound other than a color material and has a molecular weight of 2000 or more. The resin is blended for use in, for example, dispersing particles such as a pigment in a composition or for use as a binder. In addition, a resin mainly used for dispersing particles such as pigments is also referred to as a dispersant. However, such an application of the resin is an example, and the resin can be used for purposes other than this application. Further, a resin having a polymerizable group is also a component corresponding to the above-mentioned compound C.

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 5000 or more.

Examples of the resin include (meth) acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and the like. One of these resins may be used alone, or two or more of them may be used in combination. As the cyclic olefin resin, a norbornene resin can be preferably used from the viewpoint of improving heat resistance. Examples of commercially available norbornene resins include ARTON series (for example, ARTON F4520) manufactured by JSRCorporation. Further, as the resin, a resin described in examples of international publication No. WO2016/088645, a resin described in japanese patent application laid-open No. 2017-057265, a resin described in japanese patent application laid-open No. 2017-032685, a resin described in japanese patent application laid-open No. 2017-075248, and a resin described in japanese patent application laid-open No. 2017-066240 can be used, and these contents are referred to in the present description.

In the present invention, a resin having an acid group is preferably used as the resin. According to this embodiment, the developability of the photosensitive composition can be improved, and a pixel having excellent rectangularity can be easily formed. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and a carboxyl group is preferable. Resins having acid groups can be used as alkali-soluble resins, for example.

The resin having an acid group preferably includes a repeating unit having an acid group in a side chain, and more preferably includes 5 to 70 mol% of a repeating unit having an acid group in a side chain in the total repeating unit 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 resin having an acid group is preferably a resin containing a repeating unit having a carboxyl group in a side chain. Specific examples thereof include alkali-soluble phenolic resins such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolak resins, acidic cellulose derivatives having a carboxyl group in a side chain, and resins obtained by adding an acid anhydride to a polymer having a hydroxyl group. In particular, a copolymer of (meth) acrylic acid and other monomer copolymerizable therewith is preferable as the alkali-soluble resin. Examples of the other monomer copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like, and examples of the vinyl compound, examples thereof include styrene, alpha-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer. Further, as the other monomer, an N-substituted maleimide monomer described in Japanese patent application laid-open No. 10-300922, for example, N-phenylmaleimide, N-cyclohexylmaleimide, etc. can be used. The other monomer copolymerizable with these (meth) acrylic acids may be only one kind or two or more kinds. With respect to the resin having an acid group, reference can be made to the descriptions in paragraphs 0558 to 0571 of Japanese patent application laid-open No. 2012 and 208494 (corresponding to paragraphs 0685 to 0700 of U.S. patent application publication No. 2012/0235099), and the descriptions in paragraphs 0076 to 0099 of Japanese patent application laid-open No. 2012 and 198408, which are incorporated herein. Further, commercially available resins having an acid group can also be used. For example, Acrybase FF-426 (manufactured by FUJIKURAKASIEI CO., LTD.) and the like can be given.

The acid value of the resin having an acid group is preferably 30 to 200mgKOH/g for the reason that both the developability and the dispersion stability are easily achieved. The lower limit is preferably 50mgKOH/g or more, more preferably 70mgKOH/g or more, and still more preferably 100mgKOH/g or more. The upper limit is preferably not more than 180mgKOH/g, more preferably not more than 150 mgKOH/g.

The resin used in the present invention preferably further 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 may be referred to as "ether dimer").

[ chemical formula 20]

In the formula (ED1), R¹And R²Each independently represents a hydrogen atom or a C1-25 hydrocarbon group which may have a substituent.

[ chemical formula 21]

In the formula (ED2), R represents a hydrogen atom or an organic group having 1-30 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 paragraph 0317 of Japanese patent application laid-open No. 2013-029760, which is incorporated herein by reference.

The resin used in the present invention also preferably contains a repeating unit derived from a compound represented by the following formula (X).

[ chemical formula 22]

In the formula (X), R₁Represents a hydrogen atom or a methyl group, R₂Represents an alkylene group having 2 to 10 carbon atoms, R³Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer of 1 to 15.

Examples of the resin having an acid group include resins having the following structures.

[ chemical formula 23]

The photosensitive 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 in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups occupies 70 mol% or more, and more preferably a resin substantially containing only acid groups, assuming that the total amount of the acid groups and the basic groups 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 40 to 105mgKOH/g, more preferably 50 to 105mgKOH/g, and still more preferably 60 to 105 mgKOH/g. The basic dispersant (basic resin) is a resin having a larger amount of basic groups than that of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% assuming that the total amount of the acid groups and the basic groups is 100 mol%. The basic group of the basic dispersant is preferably an amino group.

The resin used as the dispersant preferably contains a repeating unit having an acid group. By using a resin as a dispersant containing a repeating unit having an acid group, the photosensitive composition can be excellent in developability, and development residue and the like can be effectively suppressed from being generated when pixels are formed by photolithography.

The resin used as a dispersant is also preferably a graft copolymer. The graft copolymer has affinity with a solvent due to the graft chain, and therefore, the pigment dispersibility and the dispersion stability with time are excellent. The details of the graft copolymer can be found in paragraphs 0025 to 0094 of Japanese patent application laid-open No. 2012 and 255128, which is incorporated herein by reference. Specific examples of the graft copolymer include the following resins. The following resins are also resins having an acid group (alkali-soluble resins). The graft copolymer includes resins described in paragraphs 0072 to 0094 of Japanese patent application laid-open No. 2012 and 255128, the contents of which are incorporated herein by reference.

[ chemical formula 24]

In the present invention, it is also preferable to use an oligoimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain as the resin (dispersant). The oligo-imine dispersant is preferably a resin having a structural unit containing a partial structure X having a functional group with pKa14 or less and a side chain containing a side chain Y having 40 to 10,000 atoms, and having a basic nitrogen atom in at least one 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. Regarding the oligoimine-based dispersant, reference is made to the descriptions in paragraphs 0102 to 0166 of Japanese patent application laid-open No. 2012 and 255128, the contents of which are incorporated herein by reference. As the oligoimine-based dispersant, a resin having the following structure or a resin described in paragraphs 0168 to 0174 of Japanese patent laid-open No. 2012 and 255128 can be used.

Also, the resin used as the dispersant is preferably a resin containing a repeating unit having an ethylenically unsaturated bond group in a side chain. The content of the repeating unit having an ethylenically unsaturated bond group in a side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and further preferably 20 to 70 mol% based on the total repeating units of the resin.

The dispersant is also available as a commercially available product, and specific examples thereof include Disperbyk-111 and 161 (manufactured by BYK Chemie GmbH). Further, the pigment dispersant described in paragraphs 0041 to 0130 of Japanese patent application laid-open No. 2014-130338 can be used, and the content thereof is incorporated in the present specification. Further, the resin having an acid group or the like can be used as the dispersant.

The content of the resin (including the content of the polymerizable polymer when the compound C includes the polymerizable polymer) in the total solid content of the photosensitive composition is preferably 10 to 50% by mass for the reason that the coating property and the curability are easily compatible. The lower limit is preferably 15% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more, from the viewpoint of easily obtaining excellent developability. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less, for the reason that a film having excellent film formability can be easily obtained.

In addition, for the reason of easy compatibility between developability and curability, the content of the resin having an acid group (including the content of the polymerizable polymer having an acid group when the compound C includes the polymerizable polymer having an acid group) in the total solid content of the photosensitive composition is preferably 7 to 45% by mass. The lower limit is preferably 12% by mass or more, more preferably 17% by mass or more, and still more preferably 22% by mass or more, from the viewpoint of easily obtaining excellent developability. From the viewpoint of easy availability of excellent curability, the upper limit is preferably 38% by mass or less, more preferably 33% by mass or less, and still more preferably 28% by mass or less.

In addition, the content of the resin having an acid group in the total amount of the resin is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more, from the viewpoint of easily obtaining excellent developability. The upper limit may be 100 mass%, 95 mass%, or 90 mass% or less.

Further, the total content of the polymerizable monomer and the resin in the total solid content of the photosensitive composition is preferably 15 to 65% by mass for the reason that curability, developability, and film formability are easily achieved at the same time. The lower limit is preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more, from the viewpoint of easily obtaining a film having excellent film formability. From the viewpoint of easy compatibility between curability and developability, the upper limit is preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less. The resin is preferably contained in an amount of 30 to 300 parts by mass based on 100 parts by mass of the polymerizable polymer. The lower limit is preferably 50 parts by mass or more, and more preferably 80 parts by mass or more. The upper limit is preferably 250 parts by mass or less, and more preferably 200 parts by mass or less.

Silane coupling agent

The photosensitive composition of the present invention may contain a silane coupling agent. According to this aspect, the adhesion between the obtained film and the support can be improved. In the present invention, the 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, (meth) allyl group, (meth) acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, thioether group, isocyanate group, and phenyl group, and amino group, (meth) acryloyl group, and 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, which are incorporated herein by reference.

The content of the silane coupling agent in the total solid content of the photosensitive 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 silane coupling agent may be one kind only, or two or more kinds. In the case of two or more types, the total amount is preferably within the above range.

Pigment derivatives

The photosensitive composition of the present invention can further contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of a pigment is substituted with an acid group, a basic group, a group having a salt structure, or a phthalimide methyl group. As the pigment derivative, a compound represented by formula (B1) is preferred.

[ chemical formula 25]

In the formula (B1), P represents a dye structure, L represents a single bond or a linking group, X represents an acid group, a basic group, a group having a salt structure, or a phthalimidomethyl group, m represents an integer of 1 or more, n represents an integer of 1 or more, and when m is 2 or more, a plurality of L and X may be different from each other, and when n is 2 or more, a plurality of X may be different from each other.

The pigment structure represented by P is preferably at least one selected from the group consisting of a pyrrolopyrrole pigment structure, a diketopyrrolopyrrole pigment structure, a quinacridone pigment structure, an anthraquinone pigment structure, a dianthraquinone pigment structure, a benzindole pigment structure, a thiazine indigo pigment structure, an azo pigment structure, a quinophthalone pigment structure, a phthalocyanine pigment structure, a naphthalocyanine pigment structure, a dioxazine pigment structure, a perylene pigment structure, a perinone pigment structure, a benzimidazolone pigment structure, a benzothiazole pigment structure, a benzimidazole pigment structure, and a benzoxazole pigment structure, and more preferably at least one selected from the group consisting of a pyrrolopyrrole pigment structure, a diketopyrrolopyrrole pigment structure, a quinacridone pigment structure, and a benzimidazolone pigment structure.

As a linking group represented by LExamples thereof include a hydrocarbon group, a heterocyclic group, -NR-, -SO₂-, -S-, -O-, -CO-, or a group composed of these combinations. R represents a hydrogen atom, an alkyl group or an aryl group.

Examples of the acid group represented by X include a carboxyl group, a sulfonic acid group, a carboxylic acid amide group, a sulfonic acid amide group, and an imide acid group. As the carboxylic acid amide group, it is preferably represented by-NHCOR^X1The group shown. As sulfonic acid amide group, preferred is a sulfonic acid amide group represented by the formula-NHSO₂R^X2The group shown. As the imide acid group, preferred is a group represented by the formula-SO₂NHSO₂R^X3、-CONHSO₂R^X4、-CONHCOR^X5or-SO₂NHCOR^X6The group shown. R^X1～R^X6Each independently represents a hydrocarbon group or a heterocyclic group. R^X1～R^X6The hydrocarbon group and the heterocyclic group may have a substituent. As a further substituent, a halogen atom is preferable, and a fluorine atom is more preferable. The basic group represented by X may be an amino group. Examples of the salt structure represented by X include salts of the above-mentioned acidic or basic groups.

Examples of the pigment derivative include compounds having the following structures. Furthermore, Japanese patent application laid-open Nos. 56-118462, 63-264674, 01-217077, 03-009961, 03-026767, 03-153780, 03-045662 and 04-285669 can also be used, the contents of the compounds described in Japanese patent application laid-open Nos. H06-145546, H06-212088, H06-240158, H10-030063, H10-195326, WO2011/024896 in paragraphs 0086-0098, WO2012/102399 in paragraphs 0063-0094, and WO2017/038252 in paragraphs 0082 are incorporated herein by reference.

[ chemical formula 26]

The content of the pigment derivative is preferably 1 to 50 parts by mass per 100 parts by mass of the pigment. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. When the content of the pigment derivative is within the above range, the dispersibility of the pigment can be improved and the aggregation of the pigment can be effectively suppressed. The pigment derivative may be used alone or in combination of two or more. When two or more are used, the total amount is preferably in the above range.

Solvents

The photosensitive composition of the present invention can contain a solvent. Examples of the solvent include organic solvents. The solvent is not particularly limited as long as it satisfies the solubility of each component or the coatability of the composition. Examples of the organic solvent include esters, ethers, ketones, and aromatic hydrocarbons. For details of these, reference can be made to paragraph 0223 of International publication WO2015/166779, which is incorporated herein by reference. 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, and propylene glycol monomethyl ether acetate. In the present invention, one kind of the organic solvent may be used alone, or two or more kinds may be used in combination. From the viewpoint of improving solubility, 3-methoxy-N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide are also preferable. However, it is sometimes preferable to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent for environmental reasons, etc. (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 organic solvents).

In the present invention, a solvent having a small metal content is preferably used, and the metal content of the solvent is preferably 10 parts per billion (ppb) or less by mass, for example. Solvents of quality ppt (parts pertrillion) grade, such as those provided by TOYO Gosei co., ltd. (journal of chemical industry, 2015, 11/13/d), may also be used as desired.

Examples of a method for removing impurities such as metals from a 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 solvent may comprise isomers (compounds of the same atomic number but different structure). The isomer may include only one kind or a plurality of kinds.

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

The content of the solvent in the photosensitive 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 addition, from the viewpoint of environmental control, the photosensitive 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 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, etc., and the amount of use and the operation method are strictly controlled. These compounds may be used as a solvent in the production of each component used in the photosensitive composition of the present invention, or may be mixed into the photosensitive composition as a residual solvent. From the viewpoint of safety to humans and environmental concerns, it is preferable to reduce these substances as much as possible. As a method for reducing the environmental controlled substance, there is a method in which the inside of the system is heated or depressurized to a boiling point of the environmental controlled substance or higher, and the environmental controlled substance is distilled from the inside of the system to be reduced. In addition, when a small amount of an environmental control substance is distilled, it is also useful to azeotropically dissolve the environmental control substance with a solvent having a boiling point equal to that of the 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 inhibit the radical polymerization reaction from proceeding and to crosslink between molecules in the distillation under reduced pressure. These distillation methods can be performed in any of the stage of the raw materials, the stage of the product (for example, a resin solution or a polyfunctional monomer solution after polymerization) obtained by reacting the raw materials, and the stage of preparing a composition by mixing these compounds.

Polymerization inhibitor

The photosensitive composition of the present invention can 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 salt (ammonium salt, cerous salt, etc.). Among them, p-methoxyphenol is preferable. The content of the polymerization inhibitor in the total solid content of the photosensitive composition is preferably 0.001 to 5% by mass.

Surface active agent

The photosensitive 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. As the surfactant, there can be mentioned paragraphs 0238 to 0245 of International publication WO2015/166779, the contents of which are incorporated herein by reference.

In the present invention, the surfactant is preferably a fluorine-based surfactant. By containing a fluorine-based surfactant in the photosensitive composition, the solution characteristics (particularly, fluidity) can be further improved, and the liquid saving properties can be further improved. Further, a film with less 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 in view of uniformity of thickness of the coating film and liquid saving, and has good solubility in the 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 to 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 3M Limited, supra), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by ASAHI GLASS CO., LTD.), PolyFox PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA Solutions Inc., supra).

Further, the fluorine-based surfactant can also suitably use an acrylic compound having a molecular structure of a functional group containing a fluorine atom, and the fluorine atom is volatilized by cleaving a portion of the functional group containing the fluorine atom when heat is applied. Examples of such a fluorine-based surfactant include MEGAFACE DS series (chemical industry journal, 2016, 2, 22 days) (sunrise industry news, 2016, 2, 23 days) manufactured by DIC Corporation, for example, MEGAFACE DS to 21.

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 preferably used. Such a fluorine-based surfactant can be 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. Examples thereof include compounds described in Japanese patent application laid-open No. 2011-89090. The fluorine-based 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 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). The following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

[ chemical formula 27]

The weight average molecular weight of the compound is preferably 3,000 to 50,000, for example, 14,000. 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 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, for example, MEGAFACE RS-101, RS-102 and RS-718K, RS-72-K manufactured by DIC Corporation. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of Japanese patent laid-open publication 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 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Limited), NCW-101, NCW-1001, NCW-1002 (manufactured by Fufillm Wako Pure Corporation), PIOND IN-6112, D-6112-W, D-6315 (manufactured by Taket & Oket Co., Ltd., ltd., ltd.), Olfine E1010, Surfynol 104, 400, 440 (manufactured by NissinChemical co., ltd.), etc.

Examples of the silicon-based surfactant include Toray Silicone DC3PA, Toray Silicone S H7PA, 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, and CheK 330 (manufactured by BYK-Mie, etc.). Further, as the silicon-based surfactant, a compound having the following structure can be used.

[ chemical formula 28]

The content of the surfactant in the total solid content of the photosensitive composition is preferably 0.001 to 5.0% by mass, and more preferably 0.005 to 3.0% by mass. The surfactant may be one kind only, or two or more kinds. In the case of two or more types, the total amount is preferably within the above range.

Ultraviolet absorbent

The photosensitive composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyl triazine compound, an indole compound, a triazine compound, or the like can be used. For details of these, reference may be made to the descriptions of paragraphs 0052 to 0072 of japanese patent application laid-open No. 2012-208374, paragraphs 0317 to 0334 of japanese patent application laid-open No. 2013-068814, and paragraphs 0061 to 0080 of japanese patent application laid-open No. 2016-162946, which are incorporated herein by reference. Specific examples of the ultraviolet absorber include compounds having the following structures. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by DAITO CHEMICAL CO., LTD.). Examples of the benzotriazole compound include mioshioil & FAT co, and the MYUA series manufactured by ltd. (journal of chemical industry, 2016, 2 months and 1 day).

[ chemical formula 29]

The content of the ultraviolet absorber in the total solid content of the photosensitive composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. In the present invention, only one kind of the ultraviolet absorber may be used, or two or more kinds thereof may be used. When two or more kinds are used, the total amount is preferably within the above range.

Antioxidant(s)

The photosensitive composition of the present invention can 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 antioxidant can be used. Preferable examples of the phenol compound include hindered phenol compounds. 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 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 suitably used. Examples of the phosphorus-based antioxidant include tris [2- [ [2,4,8, 10-tetrakis (1, 1-dimethylethyl) dibenzo [ d, f ] [1,3,2] dioxaphosphepin (dioxaphosphepin) -6-yl ] oxy ] ethyl ] amine, tris [2- [ (4,6,9, 11-tetra-tert-butyldibenzo [ d, f ] [1,3,2] dioxaphosphepin-2-yl) oxy ] ethyl ] amine, and ethyl bis (2, 4-di-tert-butyl-6-methylphenol) phosphite. Examples of commercially available antioxidants include ADKSTAAO-20, ADKSTAAO-30, ADKSTATAAO-40, ADKSTAAO-50F, ADKSTAAO-60G, ADKSTAAO-80, and ADKSTAAO-330 (manufactured by ADEKA CORPORATION).

The content of the antioxidant in the total solid content of the photosensitive composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. The antioxidant may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.

Other ingredients

The photosensitive composition of the present invention may contain, as necessary, a sensitizer, a curing accelerator, 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 perfume, a surface tension adjuster, a chain transfer agent, and the like). By appropriately containing these components, properties such as film physical properties can be adjusted. For example, the components can be described in paragraphs 0183 of Japanese patent application laid-open No. 2012 and 003225 (corresponding to paragraphs 0237 of the specification of U.S. patent application publication 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 into the present specification. The photosensitive composition of the present invention may contain a latent antioxidant, if necessary. The potential 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 heated at 80 to 200 ℃ in the presence of an acid/base catalyst to release the protecting group and function as an antioxidant. Examples of the potential antioxidant include compounds described in International publication No. WO2014/021023, International publication No. WO2017/030005, and Japanese patent application laid-open publication No. 2017-008219. Examples of commercially available products include ADEKA ARKLSGPA-5001 (manufactured by ADEKACORPORATION) and the like.

For example, when a film is formed by coating, the viscosity (23 ℃) of the photosensitive composition of the present invention is preferably 1 to 100 mPas. The lower limit is more preferably 2 mPas or more, and still more preferably 3 mPas or more. The upper limit is more preferably 50 mPas or less, still more preferably 30 mPas or less, particularly preferably 15 mPas or less.

< holding container >

The container for containing the photosensitive composition of the present invention is not particularly limited, and a known container can be used. Further, as the container, it is also preferable to use a multilayer bottle having an inner wall of the container made of 6 kinds of 6-layer resins or a bottle having a 7-layer structure of 6 kinds of resins for the purpose of suppressing impurities from being mixed into the raw material or the composition. Examples of such a container include those disclosed in Japanese patent laid-open publication No. 2015-123351.

< method for producing photosensitive composition >

The photosensitive composition of the present invention can be prepared by mixing the components. When the photosensitive composition is prepared, the total components may be dissolved or dispersed in a solvent at the same time to prepare the photosensitive composition, or two or more solutions or dispersions in which the respective components are appropriately blended may be prepared in advance as necessary, and then these may be mixed at the time of use (at the time of coating) to prepare the photosensitive composition.

When the photosensitive composition of the present invention contains particles such as a pigment, it is preferable to include a process of dispersing the particles. In the process of dispersing the particles, examples of the mechanical force used for dispersing the particles include compression, extrusion, impact, shearing, cavitation, and the like. Specific examples of these processes include bead milling, sand milling, roll milling, ball milling, paint mixer, microfluid, high-speed impeller, sand mixing, jet mixing, high-pressure wet micronization, ultrasonic dispersion, and the like. In addition, in the pulverization of the particles in the sand grinding (bead grinding), it is preferable to treat under the following conditions: the grinding efficiency is improved by using microbeads with smaller diameters and improving the filling rate of the microbeads. Further, it is preferable to remove coarse particles by filtration, centrifugal separation, or the like after the pulverization treatment. Further, as the process and the dispersing machine for dispersing the particles, those described in "published by the institute of information and distribution, japan 7 and 15, 2005" or "published by the ministry of business and development, 10.10.1978" by the published department of business and development "integrated data set of dispersion technology and industrial practice around a suspension (solid/liquid dispersion system)" can be preferably used. In addition, in the process of dispersing the particles, the particle size reduction treatment may be performed in the salt milling step. As for raw materials, facilities, treatment conditions, and the like used in the salt milling step, for example, the descriptions of japanese patent application laid-open nos. 2015-194521 and 2012-046629 can be referred to.

In the production of the photosensitive composition of the present invention, it is preferable to filter the photosensitive composition with a filter in order to remove foreign matters, reduce 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 using a fluororesin such as Polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (e.g., nylon-6, 6), a polyolefin resin (including a high-density and ultrahigh-molecular-weight polyolefin resin) such as Polyethylene and Polypropylene (PP), and the like. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable. The pore diameter of the filter is preferably about 0.01 to 7.0. mu.m, more preferably about 0.01 to 3.0. mu.m, and still more preferably about 0.05 to 0.5. mu.m. If the pore diameter of the filter is within the above range, fine foreign matter can be reliably removed. Also, a fibrous filter material is preferably used. Examples of the fibrous filter material include polypropylene fibers, nylon fibers, and glass fibers. Specifically, there may be mentioned filter elements of the ROKI TECHNO CO., LTD SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), SHPX type series (SHPX003, etc.). When filters are used, different filters (e.g., a1 st filter and a2 nd filter, etc.) may be combined. In this case, the filtration in each filter may be performed only 1 time, or 2 or more times. In addition, filters having different pore sizes may be combined within the above range. The filtration in the 1 st filter may be performed only on the dispersion, and after mixing other components, the filtration may be performed by the 2 nd filter.

< method for manufacturing optical filter >

Next, a method for producing an optical filter using the photosensitive composition of the present invention will be described. Examples of the type of the optical filter include a color filter and an infrared transmission filter.

The method for producing an optical filter of the present invention preferably includes a step of applying the photosensitive composition of the present invention to a support to form a photosensitive composition layer (photosensitive composition layer forming step), a step of exposing the photosensitive composition layer to light in pulses to form a pattern (pulse exposure step), and a step of developing and removing the photosensitive composition layer in unexposed portions to form pixels (developing step). The respective steps will be explained below.

(photosensitive composition layer Forming step)

In the photosensitive composition layer forming step, the photosensitive composition of the present invention described above is applied to a support to form a photosensitive composition layer. Examples of the support include a substrate made of a material such as silicon, alkali-free glass, soda glass, PYREX (registered trademark) glass, or quartz glass. Further, an InGaAs substrate or the like is preferably used. The support may have a Charge Coupled Device (CCD), a Complementary Metal Oxide Semiconductor (CMOS), a transparent conductive film, or the like formed thereon. In addition, a black matrix (black matrix) for separating each pixel may be formed on the support. The support may be provided with an undercoat layer as required for improving adhesion to an upper layer, preventing diffusion of a substance, or planarizing the substrate surface.

As a method of applying the photosensitive composition to the support, a known method can be used. For example, a dropping method (drop casting); slit coating method; spraying; a roll coating method; spin coating method (spin coating method); tape casting coating method; slit spin coating; a prewet method (for example, the method described in Japanese patent laid-open No. 2009-145395); various printing methods such as ink jet (for example, on-demand method, piezoelectric method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset 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 "unlimited possibility in the ink jet-patent that can be popularized and used-", published 2005-2-month, and the method shown by Sumitbe Techn Research Co., Ltd. "(particularly, pages 115 to 133), and the methods described in Japanese patent laid-open Nos. 2003-262716, 2003-185831, 2003-261827, 2012-126830, and 2006-1699325. Further, as a method for applying the photosensitive composition, the descriptions of international publication WO2017/030174 and international publication WO2017/018419 can be used, and these contents are incorporated in the present specification.

After applying the photosensitive composition to the support, further drying (prebaking) may 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 3000 seconds, more preferably 40 to 2500 seconds, and further preferably 80 to 2200 seconds. Drying can be performed using a hot plate, an oven, or the like.

(Exposure Process)

Next, the photosensitive composition layer on the support formed as described above is irradiated with light in a pulse manner to expose (pulse expose) the photosensitive composition layer in a pattern. The photosensitive composition layer is pulse-exposed through a mask having a predetermined mask pattern, whereby the photosensitive composition layer can be pulse-exposed in a pattern. Thereby, the exposed portion of the photosensitive composition layer can be cured.

The light used in the pulse exposure may be light having a wavelength of more than 300nm or light having a wavelength of 300nm or less, but is preferably light having a wavelength of 300nm or less, more preferably light having a wavelength of 270nm or less, and even more preferably light having a wavelength of 250nm or less, for the reason that more excellent curability is easily obtained. The light is preferably light having a wavelength of 180nm or more. Specifically, KrF rays (wavelength 248nm), ArF rays (wavelength 193nm) and the like are mentioned, and KrF rays (wavelength 248nm) are preferred because they facilitate obtaining more excellent curability.

The pulse exposure conditions are preferably as follows. From the viewpoint of easily instantaneously generating a large amount of active species such as radicalsIn consideration of this, 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. From the reason that the compound C is easily thermally polymerized by exposure heat, the frequency is preferably 1kHz or more, more preferably 2kHz or more, and further preferably 4kHz or more. The upper limit of the frequency is preferably 50kHz or less, more preferably 20kHz or less, and still more preferably 10kHz or less, for the reason of easily suppressing deformation of the substrate or the like due to exposure heat. From the viewpoint of curability, the maximum instantaneous illuminance is preferably 50000000W/m²Above, more preferably 100000000W/m²The above is more preferably 200000000W/m²The above. From the viewpoint of suppressing failure of high illuminance, the upper limit of the maximum instantaneous illuminance is preferably 1000000000W/m²Hereinafter, 800000000W/m is more preferable²Hereinafter, 500000000W/m is more preferable²The following. The exposure is preferably 1 to 1000mJ/cm². The upper limit is preferably 500mJ/cm²Below, more preferably 200mJ/cm²The following. The lower limit is preferably 10mJ/cm²Above, more preferably 20mJ/cm²Above, more preferably 30mJ/cm²The above.

The oxygen concentration at the time of exposure can be appropriately selected, and in addition to exposure to the atmosphere, exposure to a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially no oxygen) may be performed, or exposure to a high oxygen atmosphere having an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume) may be performed.

(developing step)

Then, the photosensitive composition layer of the unexposed portion of the photosensitive composition layer after the exposure step is removed by development to form a pixel (pattern). The photosensitive composition layer in the unexposed portion can be removed by development using a developer. Accordingly, the photosensitive composition layer in the unexposed portion is dissolved in the developer, and only the photocured portion remains on the support in the exposure step. The temperature of the developing solution is preferably 20 to 30 ℃. The developing time is preferably 20 to 180 seconds. Further, in order to improve the residue removal property, the process of throwing off the developer every 60 seconds and further supplying a new developer may be repeated a plurality of times.

The developer is preferably an alkaline aqueous solution obtained by diluting an alkaline agent in 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 alkaline agent is preferably a compound having a relatively large molecular weight in terms 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 easy transportation or storage, the developer may be temporarily prepared as a concentrated solution and diluted to a desired concentration at the time of use. The dilution ratio is not particularly limited, and may be set to a range of 1.5 to 100 times, for example. When a developer containing such an alkaline aqueous solution is used, it is preferable to wash (rinse) with pure water after development.

After the development, additional exposure treatment and heating treatment (post-baking) may be performed after the drying. The additional exposure treatment and the post-baking are post-development treatments for completely curing the film. When the additional exposure treatment is performed, the light used for the exposure is preferably light having a wavelength of 400nm or less.

The film thickness of the formed pixel (pattern) is preferably selected appropriately according to the type of pixel. For example, it is preferably not more than 2.0. mu.m, more preferably not more than 1.0. mu.m, and still more preferably 0.3 to 1.0. mu.m. The upper limit is preferably 0.8 μm or less, more preferably 0.6 μm or less. The lower limit is preferably 0.4 μm or more.

The size (line width) of the formed pixel (pattern) is preferably selected as appropriate according to the application and the type of pixel. For example, it is preferably 2.0 μm or less. The upper limit is preferably 1.0 μm or less, more preferably 0.9 μm or less. The lower limit is preferably 0.4 μm or more.

When a filter having a plurality of types of pixels is manufactured, at least one type of pixel may be formed through the above-described steps, and a pixel to be formed first (a 1 st type pixel) is preferably formed through the above-described steps. The pixels formed in the 2 nd and subsequent stages (pixels in the 2 nd and subsequent stages) may be formed through the same steps as described above, or may be formed by exposure to continuous light.