JP2009265518A - Photosensitive composition, photosensitive composition for solid-state imaging element, light-shielding color filter for solid-state imaging element, and solid-state imaging element - Google Patents

Abstract

Provided is a photosensitive composition having a light-shielding property in a wide range from the ultraviolet region to the infrared region, having a high sensitivity, and having few side edges, and a photosensitive composition for a solid-state imaging device using the same. A light-shielding color filter for a solid-state imaging device and a solid-state imaging device are provided.
(A) a polymerizable compound, (B) a binder polymer, (C) a photopolymerization initiator, and (D) a titanium black dispersion, and (A) a polymerizable compound / (B) a binder polymer. A photosensitive composition having a mass ratio of 1.0 or less.
[Selection figure] None

Description

  The present invention relates to a photosensitive composition, a photosensitive composition for a solid-state imaging device, a light-shielding color filter for a solid-state imaging device, and a solid-state imaging device.

A color filter used in a liquid crystal display device is provided with a light-shielding color filter called a black matrix for the purpose of shielding light between colored pixels and improving contrast. A solid-state image sensor is also provided with a light-shielding color filter for the purpose of preventing noise and improving image quality.
A photosensitive resin composition containing a black color material such as carbon black or titanium black is known as a composition for forming a black matrix for a liquid crystal display device or a light-shielding color filter for a solid-state imaging device. (For example, see Patent Documents 1 to 5).

The black matrix for liquid crystal display devices is mainly required to block light in the visible region, whereas the light-blocking color filter for solid-state imaging devices has light blocking properties in the infrared region in addition to the light blocking property in the visible region. It is necessary to prepare.
While the black matrix for liquid crystal display devices is required to be miniaturized, the light-shielding color filter for solid-state image sensors (especially, the surface opposite to the light-receiving element forming surface of the support (hereinafter referred to as “back surface”). The light-shielding color filter for shielding light) is required to uniformly shield light over a larger area than the black matrix for liquid crystal display devices.

As a light-shielding color filter for a solid-state image sensor, a light-shielding color filter with a wide area was formed using a photosensitive composition using a black pigment such as carbon black used in the black matrix of the conventional liquid crystal display device and the like. In this case, it is necessary to shield light having a wavelength of 800 to 1300 nm in order to prevent noise generation as well as light shielding property in the visible region. In this case, if carbon black is used for curing by exposure to ultraviolet rays or the like, the transmittance in the wavelength region of 300 to 500 nm is extremely low and curing is difficult. Titanium black has a higher light-shielding property in the infrared region than carbon black, and has a transmittance of 300 to 500 nm higher than that of carbon black. However, the transmittance is insufficient, resulting in insufficient curing and sensitivity. Lower. Increasing the polymerizable compound, which is a polymerizable component, in order to ensure the sensitivity increases the sensitivity, but in the vicinity of the substrate, the transmittance at a wavelength of 300 to 500 nm is low, and curing by polymerization does not easily proceed. For this reason, there is a problem that the vicinity of the exposed substrate is also developed in the developing step, and a phenomenon that the thickness of the light-shielding color filter surface and the thickness of the film in the vicinity of the substrate are different, so-called side edges are likely to enter.
Japanese Patent Laid-Open No. 10-246955 JP-A-9-54431 Japanese Patent Laid-Open No. 10-46042 JP 2006-36750 A JP 2007-115921 A

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, the present invention is a light-shielding color filter for a solid-state imaging device that has a light-shielding property in a wide range from the ultraviolet region to the infrared region, can form a high-definition pattern with high sensitivity, and few side edges. An object of the present invention is to provide a photosensitive composition useful for the formation of the above.
Another object of the present invention is to provide a solid-state imaging having a colored pattern that is fine and achieves light-shielding properties in a wide range from the ultraviolet region to the infrared region by using the photosensitive composition of the present invention. An object of the present invention is to provide a light-shielding color filter for an element and a solid-state imaging device including the same and having reduced noise and improved image quality.

As a result of intensive studies, the present inventor has found that the above-described problems can be achieved by the following means.
<1> Mass of (A) polymerizable compound, (B) binder polymer, (C) photopolymerization initiator, and (D) titanium black dispersion, and (A) polymerizable compound / (B) binder polymer A photosensitive composition having a ratio of 1.0 or less.

<2> The photosensitive composition according to <1>, wherein the (C) photopolymerization initiator is an oxime compound.
<3> The photosensitive composition according to <1> or <2>, wherein the (B) binder polymer is a compound having a polymerizable group in a side chain.
<4> The photosensitive composition according to any one of <1> to <3>, wherein a content of the titanium black is in a range of 40 to 85 mass% with respect to a total solid content of the photosensitive composition. object.

<5> A photosensitive composition for a solid-state imaging device, comprising the photosensitive composition according to any one of <1> to <4>.
<6> A light-shielding color filter for a solid-state imaging device having a colored pattern formed on the support using the photosensitive composition for a solid-state imaging device according to <5>.
<7> A solid-state imaging device comprising the light-shielding color filter for a solid-state imaging device according to <6>.

According to the present invention, the light-shielding color filter for a solid-state imaging device has a light-shielding property in a wide range from the ultraviolet region to the infrared region, and can form a high-definition pattern with high sensitivity and few side edges. A photosensitive composition useful for the formation of can be provided.
Further, according to the present invention, by using the photosensitive composition, the light-shielding property for a solid-state imaging device having a fine color pattern that achieves light-shielding properties in a wide range from the ultraviolet region to the infrared region. It is possible to provide a color filter and a solid-state imaging device including the color filter and having reduced noise and improved image quality.

The present invention comprises (A) a polymerizable compound, (B) a binder polymer, (C) a photopolymerization initiator, and (D) a titanium black dispersion, and (A) a polymerizable compound / (B) a binder polymer. It is a photosensitive composition having a mass ratio of 1.0 or less.
Hereinafter, the best mode for carrying out the invention will be described in detail.

<(A) Polymerizable compound>
The polymerizable compound that can be used in the present invention has at least one functional group that can react with a radical and / or acid generated by light, and has a cyclic ether and an ethylenically unsaturated double bond. In view of reactivity and gelation efficiency, a compound having an ethylenically unsaturated double bond is preferable, and it is preferable to have two or more functional groups in one molecule. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention.

  These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used.

  Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

(However, in the general formula (a), R ⁹¹ and R ⁹² each represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Furthermore, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238, In addition, a photosensitive composition excellent in photosensitive speed can be obtained.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these addition polymerizable compounds, the details of usage methods such as the structure, single use or combination, addition amount and the like can be arbitrarily set according to the final performance design of the photosensitive composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
In addition, the addition polymerizable compound also has compatibility and dispersibility with other components (eg, photopolymerization initiator, colorant (pigment, dye), binder polymer, etc.) contained in the photosensitive composition. The selection and use method is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a support.

  Examples of polymerizable compounds that can be specifically used in the present application include bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylol. Ethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate Sorbitol pentaacrylate, sorbitol Preferred examples include saacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate modified EO, dipentaerythritol hexaacrylate EO modified, and urethane oligomer UAS-10, UAB-140 (Sanyo National Policy) Pulp Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

  In addition, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.

The polymerizable compound in the present application refers to a low molecular compound having a molecular weight of 1000 or less, and a preferable polymerizable compound has a bifunctional or higher functional group, preferably a trifunctional or higher functional group, more preferably a tetrafunctional or higher functional group. preferable. Moreover, since the photosensitive composition of this application controls developability and a sensitivity, it is possible to mix 2 or more types.
As content of the polymeric compound in a photosensitive composition, it is 1-50 mass% as solid content in a photosensitive composition, Preferably, it is 3-40 mass%, More preferably, it is 5-25 mass%. . Within this range, the reactivity and gelation efficiency are good.

<(B) Binder polymer>
A binder polymer can be used for the purpose of developing property control, polymerizability control, film property improvement and the like. As the binder polymer of the present invention (hereinafter appropriately referred to as a specific binder), it is preferable to use a linear organic polymer. As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a resin obtained by homo- or copolymerization of a monomer having a carboxyl group, acid anhydride Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. It is done. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

Further, as the acid group, an alkali-soluble resin can be synthesized using a monomer having a sulfonic acid group or a monomer having a phosphate ester and used in the present invention.
Examples of the phosphoric acid ester type monomer include Phosmer PE, Phosmer M, Phosmer PP, Phosmer CL, and Phosmer MH manufactured by Unichemical Co., Ltd. Examples of the monomer having sulfonic acid include vinyl sulfonic acid, 3-sulfopropyl methacrylate potassium salt, 3-sulfopropyl acrylate potassium salt, and 2-acrylamido-2-methyl-1-propanesulfonic acid.

  When an alkali-soluble resin is used as a copolymer, a monomer other than the above-mentioned monomers can be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic esters having an aliphatic hydroxyl group such as methacrylic esters.
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane polymers containing acid groups described in No. 271741, Japanese Patent Application No. 10-116232, and urethane polymers having acid groups and double bonds in side chains described in JP-A No. 2002-107918, Since it has excellent adhesion strength, it is advantageous in terms of suitability for low exposure.
In addition, the acetal-modified polyvinyl alcohol polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability.

  In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight of the specific binder that can be used in the present invention is preferably 3000 or more, more preferably 5,000 to 300,000, and the number average molecular weight is preferably 3,000 or more, and more preferably. Is in the range of 4000-250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
These binder polymers may be any of random polymers, block polymers, graft polymers and the like.

The specific binder that can be used in the present invention can be synthesized by a conventionally known method. Solvents used in the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used when synthesizing a specific binder that can be used in the photosensitive composition include known compounds such as an azo-based initiator, a peroxide initiator, and a thiol compound.

In the present invention, the preferred specific binder is preferably a polymer having an ethylenically polymerizable group in the side chain from the viewpoint of sensitivity, and the preferred polymerizable group has an allyl group, a methacrylic ester group, an acrylic ester group, or a styryl group. It is preferable.
The most preferred binder for the present invention is a polymer having an acid group and a polymerizable group in the side chain. The side chain double bond can be obtained, for example, by adding an ethylenically unsaturated group-containing epoxy compound to the carboxyl group of an alkali-soluble resin having a carboxyl group.

  As the polymer having a carboxyl group, 1) a polymer obtained by radical polymerization or ion polymerization of a monomer having a carboxyl group, and 2) radical or ion polymerization of a monomer having an acid anhydride to hydrolyze or half-esterify the acid anhydride unit. And 3) an epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride.

  Specific examples of vinyl resins having a carboxyl group include (meth) acrylic acid, 2-succinoloyloxyethyl methacrylate, 2-malenoyloxyethyl methacrylate, and methacrylic acid 2 as monomers having a carboxyl group. -Resins obtained by homopolymerizing unsaturated carboxylic acids such as phthaloyloxyethyl, 2-hexahydrophthaloyloxyethyl methacrylate, maleic acid, fumaric acid, itaconic acid, and crotonic acid, and these unsaturated carboxylic acids as styrene , Α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide Glycidyl (meth) acrylate, Lylglycidyl ether, glycidyl ethyl acrylate, glycidyl crotonic acid ether, (meth) acrylic acid chloride, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylolacrylamide, N, N-dimethylacrylamide, N-methacryloylmorpholine , N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethylacrylamide, and other resins copolymerized with a vinyl monomer having no carboxyl group.

In addition, maleic anhydride is copolymerized with styrene, α-methylstyrene, etc., and the maleic anhydride unit part is half-esterified with monohydric alcohol such as methanol, ethanol, propanol, butanol, hydroxyethyl (meth) acrylate, or water. A hydrolyzed resin is also mentioned.
It can also be obtained by reacting a resin having an epoxy group with a compound having a nucleophilic group and a polymerizable group. The polymer of the present invention can also be obtained by reacting a polymer obtained by copolymerizing glycidyl methacrylate with acrylic acid, methacrylic acid, hydroxyethyl methacrylate, or the like. In this case, although the acid value may be lowered, an acid such as succinic acid, maleic anhydride, cyclohexanedicarboxylic acid anhydride, itaconic acid anhydride, etc. may be added to the hydroxyl group generated by the reaction between the epoxy group and the carboxylic acid. A polymer having a desired acid value can be obtained by reacting with an anhydride.

  In addition, (meth) acrylic acid, 2-succinoloyloxyethyl methacrylate, 2-malenoyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, methacrylic acid, such as novolak-type epoxy acrylate resin and bisphenol-type epoxy resin After adding unsaturated carboxylic acid such as 2-hexahydrophthaloyloxyethyl acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, or saturated carboxylic acid such as acetic acid, propionic acid, stearic acid, etc., maleic anhydride And resins modified with acid anhydrides such as itaconic anhydride, tetrahydrophthalic anhydride, and phthalic anhydride.

  Among the above, from the viewpoint of developability, a resin having a carboxyl group, in particular, a (meth) acrylic acid (co) polymer resin containing (meth) acrylic acid is preferable. Specific examples of these copolymers include Examples thereof include a methyl methacrylate / methacrylic acid copolymer described in JP-A-60-208748, a methyl methacrylate / methyl acrylate / methacrylic acid copolymer described in JP-A-60-214354, Benzyl methacrylate / methyl methacrylate / methacrylic acid / 2-ethylhexyl acrylate copolymer described in Kaihei 5-36581, methyl methacrylate / n-butyl methacrylate / acrylic acid 2 described in JP-A-5-333542 -Ethylhexyl / methacrylic acid copolymer, styrene / methacrylic described in JP-A-7-261407 Methyl / methyl acrylate / methacrylic acid copolymer, methyl methacrylate / n-butyl acrylate / 2-ethylhexyl acrylate / methacrylic acid copolymer described in JP-A-10-110008, JP-A-10-198031 Examples thereof include methyl methacrylate / n-butyl acrylate / 2-ethylhexyl acrylate / styrene / methacrylic acid copolymer.

An unsaturated group can also be introduce | transduced into the polymer which has a carboxylic acid group using an unsaturated epoxy compound.
As such an unsaturated epoxy compound, those having a glycidyl group as an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether can be used, but preferred are unsaturated compounds having an alicyclic epoxy group. is there. Examples of such compounds include the following compounds.

Epoxy ring introduction reaction into the resin side chain includes, for example, tertiary amines such as triethylamine, benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, pyridine, triphenylphosphine Etc. as a catalyst in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours. When the amount of the introduced alicyclic epoxy unsaturated compound is controlled so that the acid value of the obtained resin satisfies the range of 5 to 250 KOH · mg / g, it is preferable in terms of alkali developability. The molecular weight is preferably in the range of 3000 to 3000000, more preferably 5000 to 100,000 in terms of weight average.

  The specific binder in the present invention is preferably a polymer having at least one selected from structural units represented by any one of the following general formulas (i) to (iii) as an unsaturated double bond moiety.

In the general formulas (i) to (iii), A ¹ , A ² , and A ³ each independently represent an oxygen atom, a sulfur atom, or —N (R ³⁰ ) —, and R ³⁰ represents a substituent. It represents an alkyl group that may have. G ¹ , G ² , and G ³ each independently represent a divalent organic group. Y ¹ and Y ² each independently represent an oxygen atom, a sulfur atom, or —N (R ²⁹ ) —, and R ²⁹ represents an alkyl group which may have a substituent. Y ³ represents an oxygen atom, a sulfur atom, an optionally substituted phenylene group, or —N (R ²⁸ ) —, and R ²⁸ represents an optionally substituted alkyl group. R ^{31 to} R ⁵⁰ each independently represents a monovalent substituent.

In the general formula (i), R ^{31 to} R ³³ each independently represents a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may further have a substituent. Among them, R ³¹ , R ³² is preferably a hydrogen atom, and R ³³ is preferably a hydrogen atom or a methyl group.
R ^{34 to} R ³⁶ each independently represents a monovalent substituent. Examples of R ³⁴ include a hydrogen atom or an alkyl group which may further have a substituent. Among them, a hydrogen atom or a methyl group An ethyl group is preferred. R ³⁵ and R ³⁶ each independently further have a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group that may further have a substituent, or a substituent. An aryl group which may further have a substituent, an aryloxy group which may further have a substituent, an alkylsulfonyl group which may further have a substituent, and further having a substituent An arylsulfonyl group which may be substituted may be mentioned. Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may further have a substituent, and an aryl group which may further have a substituent are preferable.
Here, examples of the substituent that can be introduced include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.

A ¹ represents an oxygen atom, a sulfur atom, or —N (R ³⁰ ) —, and Y ¹ represents an oxygen atom, a sulfur atom, or —N (R ²⁹ ) —. Here, examples of R ²⁹ and R ³⁰ include an alkyl group which may have a substituent.
G ¹ represents a divalent organic group, but an alkylene group which may have a substituent is preferable. More preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, or a substituent having 6 to 20 carbon atoms. An aromatic group that may be present may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms that may have a substituent, or cyclo that may have a substituent having 3 to 10 carbon atoms. An alkylene group and an aromatic group which may have a substituent having 6 to 12 carbon atoms are preferable in terms of performance such as strength and developability.
Here, a hydroxyl group is preferable as the substituent in G ¹ .

In the general formula (ii), R ^{37 to} R ³⁹ each independently represents a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may further have a substituent. Among them, R ³⁷ , R ³⁸ is preferably a hydrogen atom, and R ³⁹ is preferably a hydrogen atom or a methyl group.
R ^{40 to} R ⁴² each independently represents a monovalent substituent. Specific examples of the substituent include a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, and a nitro group. , A cyano group, an alkyl group which may further have a substituent, an aryl group which may further have a substituent, an alkoxy group which may further have a substituent, and an aryl which may further have a substituent Examples thereof include an oxy group, an alkylsulfonyl group that may further have a substituent, and an arylsulfonyl group that may further have a substituent. Among them, a hydrogen atom, an alkoxycarbonyl group, and a substituent may be further included. A good alkyl group and an aryl group which may further have a substituent are preferred.
Here, examples of the substituent that can be introduced include those exemplified in the general formula (i).

A ² each independently represents an oxygen atom, a sulfur atom, or —N (R ³⁰ ) —, where R ³⁰ includes a hydrogen atom, an alkyl group that may have a substituent, and the like. Can be mentioned.
G ² represents a divalent organic group, but an alkylene group which may have a substituent is preferable. Preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, and a substituent which has 6 to 20 carbon atoms. Aromatic group, etc. may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cycloalkylene which may have a substituent having 3 to 10 carbon atoms. Group, and an aromatic group which may have a substituent having 6 to 12 carbon atoms is preferable in terms of performance such as strength and developability.
Here, the substituent in G ² is preferably a hydroxyl group.

Y ² represents an oxygen atom, a sulfur atom, —N (R ²⁹ ) — or a phenylene group which may have a substituent. Here, examples of R ²⁹ include a hydrogen atom and an alkyl group which may have a substituent.

In the general formula (iii), R ^{43 to} R ⁴⁵ each independently represents a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among them, R ⁴³ , R ⁴⁴ is preferably a hydrogen atom, and R ⁴⁵ is preferably a hydrogen atom or a methyl group.
R ^{46 to} R ⁵⁰ each independently represents a monovalent substituent. R ^{46 to} R ⁵⁰ are, for example, a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, a nitro group, or a cyano group. , An alkyl group that may further have a substituent, an aryl group that may further have a substituent, an alkoxy group that may further have a substituent, an aryloxy group that may further have a substituent, Examples include an alkylsulfonyl group that may further have a substituent, an arylsulfonyl group that may further have a substituent, and the like. Among them, a hydrogen atom, an alkoxycarbonyl group, and an alkyl group that may further have a substituent An aryl group which may further have a substituent is preferable. Examples of the substituent that can be introduced include those listed in the general formula (i).
A ³ represents an oxygen atom, a sulfur atom, or —N (R ³⁰ ) —, and Y ³ represents an oxygen atom, a sulfur atom, or —N (R ²⁸ ) —. Examples of R ²⁸ and R ³⁰ include the same as those in general formula (i).

G ³ represents a divalent organic group, and an alkylene group which may have a substituent is preferable. Preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, and a substituent which has 6 to 20 carbon atoms. Aromatic group, etc. may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cycloalkylene which may have a substituent having 3 to 10 carbon atoms. Group, and an aromatic group which may have a substituent having 6 to 12 carbon atoms is preferable in terms of performance such as strength and developability.
Here, the substituent in G ³ is preferably a hydroxyl group.

  As the specific binder in the present invention, the structural unit represented by the general formulas (i) to (iii) is 20 mol% or more and less than 95 mol% in one molecule from the viewpoint of improving curability and reducing development residue. A compound included in the range is preferable. More preferably, it is 25-90 mol%. More preferably, it is the range of 30 mol% or more and less than 85 mol%.

  The synthesis of the polymer compound having the structural unit represented by the general formulas (i) to (iii) is based on the synthesis method described in paragraphs [0027] to [0057] of JP-A-2003-262958. Can be done. Among them, the synthesis method 1) in the same publication is preferable, and this is shown in the following (1).

  Specific examples of the polymer compound having the structural units represented by the general formulas (i) to (iii) include the following polymer compounds 1 to 17.

Moreover, the resin obtained by the synthesis method of the following (1) or (2) can be mentioned suitably.
(1) A structure using the compound represented by the following general formula (iv) as a copolymerization component, withdrawing protons using a base, desorbing L, and the structure represented by the general formula (i) A method for obtaining a desired polymer compound having
In general formula (iv), L represents an anionic leaving group, and preferred examples include a halogen atom and a sulfonic acid ester. R ^{33 to} R ³⁶ , A ¹ , G ¹ , and Y ¹ have the same meaning as in the general formula (i), and the base used for causing the elimination reaction may be either an inorganic compound or an organic compound. May be used. Details and preferred embodiments of this method are described in paragraphs [0028] to [0033] of JP-A No. 2003-262958.

  Preferred inorganic compound bases include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like, and organic compound bases include sodium methoxide, sodium ethoxide, potassium t- Examples thereof include metal alkoxides such as butoxide, organic amine compounds such as triethylamine, pyridine and diisopropylethylamine.

(2) the following general formula to a polymer with a compound represented by as a copolymer component in (v), the base treatment is rise to elimination reaction to a specific functional group to remove X ^10, radical reactive groups How to get.
In general formula (v), A ⁵ represents an oxygen atom, a sulfur atom, or —N (R ⁵⁴ ) —, A ⁶ represents an oxygen atom, a sulfur atom, or —NR ⁵⁸ —, and R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , and R ⁵⁸ each independently represent hydrogen or a monovalent organic group, X ¹⁰ represents a group to be removed by elimination reaction, and G ⁵ represents an organic linking group. n represents an integer of 1 to 10. Details and preferred embodiments of this method are described in detail in JP-A No. 2003-335814.

  Examples of the resin obtained by the synthesis method (2) include a polymer compound described in JP-A-2003-335814, specifically, for example, (i) a polyvinyl polymer compound, and (ii) a polyurethane polymer. Compound, (iii) polyurea polymer compound, (iv) poly (urethane-urea) polymer compound, (v) polyester polymer compound, (vi) polyamide polymer compound, (vii) acetal-modified polyvinyl alcohol Preferred examples include high-molecular compounds of the system and specific compounds obtained from the respective descriptions.

  Examples of the compound represented by the general formula (iv) include the following compounds (M-1) to (M-12), but are not limited thereto.

  Next, examples (i-1 to i-52) of the compounds represented by the general formula (v) are listed below.

The specific binder in the present invention preferably has a photopolymerizable unsaturated bond from the viewpoint of improving exposure sensitivity. From the viewpoint of enabling alkali development, COOH, SO ₃ H, PO ₃ H ₂ , OSO ₃ H, OPO ₂ H ₂ are preferable. The specific binder in the present invention has an acid value of 5 to 250 mgKOH / g, preferably 40 to 200, more preferably 60 to 150 from the viewpoint of dispersion stability, balance between developability and sensitivity. Is preferred.
Examples of monofunctional monomers that can be used as the copolymerization monomer when synthesizing the specific binder in the present invention include the following in addition to (1) to (12) described in paragraphs [0030] to [0033]. (13).

  (13) Monomers having a carboxy group such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene, and acidic cellulose derivatives having a carboxy group in the side chain can also be used.

  Moreover, in this invention, the non-acrylic resin which has a polymeric group in a side chain other than the said (meth) acrylic-type resin can also be used.

Specific examples of such specific binder polymers include urethane resins, novolak resins, acetal resins, styrene resins, polyester resins, polyamide resins, polyurea resins, polyimide resins each having an ethylenically unsaturated bond in the side chain. Among these, urethane resins (hereinafter referred to as “specific urethane resins” as appropriate) and styrene resins (hereinafter referred to as “specific styrene resins” as appropriate) are particularly preferable from the viewpoint of effects.
First, a specific urethane resin which is a preferred embodiment of the present invention will be described in detail.

(Urethane resin having ethylenically unsaturated bonds in the side chain)
Specific urethane resins used in the present invention include those having at least one of functional groups represented by the following general formulas (1) to (3) in the side chain. First, the functional groups represented by the following general formulas (1) to (3) will be described.

In the general formula (1), R ^{1 to} R ³ each independently represents a hydrogen atom or a monovalent organic group, and R ¹ is preferably a hydrogen atom or an alkyl which may have a substituent. A hydrogen atom and a methyl group are preferable because of high radical reactivity. R ² and R ³ are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, or a substituted group. An aryl group which may have a group, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, and a substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a substituent An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable because of high radical reactivity.

X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —, and R ¹² represents a hydrogen atom or a monovalent organic group. Here, examples of R ¹² include an alkyl group which may have a substituent. Among them, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.

  Here, examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylamino group, an arylamino group, a carboxyl group, an alkoxycarbonyl group, A sulfo group, a nitro group, a cyano group, an amide group, an alkylsulfonyl group, an arylsulfonyl group and the like can be mentioned.

In the general formula (2), R ^{4 to} R ⁸ each independently represents a hydrogen atom or a monovalent organic group, and R ^{4 to} R ⁸ are preferably a hydrogen atom, a halogen atom, an amino group, or a dialkyl. Amino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy which may have a substituent A group, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, Examples include an arylsulfonyl group that may have a substituent. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group that may have a substituent, and an aryl group that may have a substituent. Lumpur group.

Examples of the substituent that can be introduced are the same as those in the general formula (1). Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. R < ¹² > is synonymous with the case of R < ¹² > of General formula (1), and its preferable example is also the same.

In the general formula (3), R ⁹ is preferably a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom or a methyl group has high radical reactivity. To preferred. R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl group that may have a substituent. An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, a substituent An arylamino group that may have, an alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, and the like, among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable because of high radical reactivity.

Here, examples of the substituent that can be introduced are the same as those in the general formula (1). Further, Z is an oxygen atom, a sulfur atom, -N ^{(R 13)} -, or a phenylene group which may have a substituent. Examples of R ¹³ include an alkyl group which may have a substituent. Among them, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.

Next, the basic skeleton of the specific urethane resin according to the present invention will be described.
The specific urethane resin according to the present invention is represented by a reaction product of at least one diisocyanate compound represented by the following general formula (4) and at least one diol compound represented by the general formula (5). A polyurethane resin having a structural unit as a basic skeleton (hereinafter, referred to as “specific polyurethane resin” as appropriate).

In General Formulas (4) and (5), X ⁰ and Y ⁰ each independently represent a divalent organic residue.

  At least one of the diisocyanate compound represented by the general formula (4) or the diol compound represented by the general formula (5) is at least one of the groups represented by the general formulas (1) to (3). If it has one, as a reaction product of the diisocyanate compound and the diol compound, a specific polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain is generated. Is done. According to this method, the specific polyurethane resin according to the present invention can be produced more easily than the substitution and introduction of a desired side chain after the reaction of the polyurethane resin.

1) Diisocyanate compound The diisocyanate compound represented by the general formula (4) is obtained by, for example, subjecting a triisocyanate compound to 1 equivalent of a monofunctional alcohol or monofunctional amine compound having an unsaturated group. There are products that are produced.
Examples of the triisocyanate compound include those shown below, but are not limited thereto.

  Examples of the monofunctional alcohol or monofunctional amine compound having an unsaturated group include those shown below, but are not limited thereto.

  Here, as a method for introducing an unsaturated group into the side chain of the polyurethane resin, a method using a diisocyanate compound containing an unsaturated group in the side chain as a raw material for producing the polyurethane resin is suitable. Examples of the diisocyanate compound obtained by addition reaction of a triisocyanate compound and a monofunctional alcohol having an unsaturated group or 1 equivalent of a monofunctional amine compound having an unsaturated group in the side chain include, for example, Although the following are mentioned, it is not limited to this.

  The specific polyurethane resin used in the present invention includes, for example, the above-described diisocyanate compound containing an unsaturated group from the viewpoint of improving compatibility with other components in the photosensitive composition and improving storage stability. Other diisocyanate compounds can be copolymerized.

  Examples of the diisocyanate compound to be copolymerized include the following. Preferred is a diisocyanate compound represented by the following general formula (6).

In General Formula (6), L ¹ represents a divalent aliphatic or aromatic hydrocarbon group which may have a substituent. If necessary, L ¹ may have another functional group that does not react with an isocyanate group, such as an ester, urethane, amide, or ureido group.

Specific examples of the diisocyanate compound represented by the general formula (6) include those shown below.
That is, 2,4-tolylene diisocyanate, 2,4-tolylene diisocyanate dimer, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate Aromatic diisocyanate compounds such as 1,5-naphthylene diisocyanate, 3,3′-dimethylbiphenyl-4,4′-diisocyanate;
Aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate and the like;
Alicyclic diisocyanate compounds such as isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane;
And a diisocyanate compound which is a reaction product of a diol and a diisocyanate such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate.

2) Diol Compound As the diol compound represented by the general formula (5), a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, and the like are widely used.

  Here, as a method for introducing an unsaturated group into the side chain of the polyurethane resin, in addition to the above-described method, a method using a diol compound containing an unsaturated group in the side chain as a raw material for producing the polyurethane resin is also suitable. is there. Such a diol compound may be a commercially available one such as trimethylolpropane monoallyl ether, a halogenated diol compound, a triol compound, an aminodiol compound, a carboxylic acid containing an unsaturated group, and an acid. It may be a compound that is easily produced by a reaction with a chloride, isocyanate, alcohol, amine, thiol, or alkyl halide compound. Specific examples of these compounds include, but are not limited to, the compounds shown below.

  Further, as a more preferable binder polymer in the present invention, it was obtained by using a diol compound represented by the following general formula (G) as at least one diol compound having an ethylenically unsaturated bond group in the synthesis of polyurethane. Mention may be made of polyurethane resins.

In the general formula (G), R ^{1 to} R ³ each independently represents a hydrogen atom or a monovalent organic group, A ⁰ represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) — is represented, and R ¹² represents a hydrogen atom or a monovalent organic group.
Incidentally, ^R 1 to R ³ and X in the general formula (G) has the same meaning as ^R 1 to R ³ and X in the general formula (1), preferred embodiments versa.
By using a polyurethane resin derived from such a diol compound, it is considered that the coating strength of the layer can be improved by suppressing the excessive molecular motion of the polymer main chain caused by the secondary alcohol having a large steric hindrance. It is done.
Hereinafter, specific examples of the diol compound represented by the general formula (G) which are suitably used for the synthesis of the specific polyurethane resin will be shown.

The specific polyurethane resin used in the present invention is, for example, a diol compound containing the above unsaturated group from the viewpoint of improving compatibility with other components in the photosensitive composition and improving storage stability. Diol compounds other than can be copolymerized.
Examples of such diol compounds include the polyether diol compounds, polyester diol compounds, and polycarbonate diol compounds described above.

  Examples of the polyether diol compound include compounds represented by the following formulas (7), (8), (9), (10), and (11), and random copolymerization of ethylene oxide and propylene oxide having a hydroxyl group at the terminal. Coalescence is mentioned.

In formulas (7) to (11), R ¹⁴ represents a hydrogen atom or a methyl group, and X ¹ represents the following group. Moreover, a, b, c, d, e, f, and g each represent an integer of 2 or more, and preferably an integer of 2 to 100.

Specific examples of the polyether diol compound represented by the above formulas (7) and (8) include the following.
That is, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-1,2-propylene glycol, tri-1,2-propylene glycol, tetra-1, 2-propylene glycol, hexa-1,2-propylene glycol, di-1,3-propylene glycol, tri-1,3-propylene glycol, tetra-1,3-propylene glycol, di-1,3-butylene glycol, Tri-1,3-butylene glycol, hexa-1,3-butylene glycol, polyethylene glycol having a weight average molecular weight of 1000, polyethylene glycol having a weight average molecular weight of 1500, poly having a weight average molecular weight of 2000 Tylene glycol, polyethylene glycol with a weight average molecular weight of 3000, polyethylene glycol with a weight average molecular weight of 7500, polypropylene glycol with a weight average molecular weight of 400, polypropylene glycol with a weight average molecular weight of 700, polypropylene glycol with a weight average molecular weight of 1000, polypropylene glycol with a weight average molecular weight of 2000 , Polypropylene glycol having a weight average molecular weight of 3000, polypropylene glycol having a weight average molecular weight of 4000, and the like.

Specific examples of the polyether diol compound represented by the formula (9) include those shown below.
That is, Sanyo Chemical Industries, Ltd. (trade name) PTMG650, PTMG1000, PTMG2000, PTMG3000, and the like.

Specific examples of the polyether diol compound represented by the formula (10) include those shown below.
That is, Sanyo Chemical Industries, Ltd., (trade name) New Pole PE-61, New Pole PE-62, New Pole PE-64, New Pole PE-68, New Pole PE-71, New Pole PE-74, New Pole PE-75, New Pole PE-78, New Pole PE-108, New Pole PE-128, New Pole PE-61, and the like.

Specific examples of the polyether diol compound represented by the formula (11) include those shown below.
That is, Sanyo Chemical Industries, Ltd. (trade name) New Pole BPE-20, New Pole BPE-20F, New Pole BPE-20NK, New Pole BPE-20T, New Pole BPE-20G, New Pole BPE-40, New Pole BPE-60, New Pole BPE-100, New Pole BPE-180, New Pole BPE-2P, New Pole BPE-23P, New Pole BPE-3P, New Pole BPE-5P, and the like.

Specific examples of the random copolymer of ethylene oxide and propylene oxide having a hydroxyl group at the terminal include the following.
That is, Sanyo Chemical Industries, Ltd. (trade name) New Pole 50HB-100, New Pole 50HB-260, New Pole 50HB-400, New Pole 50HB-660, New Pole 50HB-2000, New Pole 50HB-5100, etc. It is.

  Examples of the polyester diol compound include compounds represented by formulas (12) and (13).

In formulas (12) and (13), L ² , L ³ and L ⁴ may be the same or different and each represents a divalent aliphatic or aromatic hydrocarbon group, and L ⁵ represents a divalent aliphatic carbonization. Represents a hydrogen group. Preferably, L ^{2 to} L ⁴ each represent an alkylene group, an alkenylene group, an alkynylene group, or an arylene group, and L ⁵ represents an alkylene group. In addition, other functional groups that do not react with the isocyanate group, such as ether, carbonyl, ester, cyano, olefin, urethane, amide, ureido group, or halogen atom may be present in L ^{2 to} L ⁵ . n1 and n2 are each an integer of 2 or more, preferably an integer of 2 to 100.
As the polycarbonate diol compound, there is a compound represented by the formula (14).

In the formula (14), L ⁶ may be the same or different and each represents a divalent aliphatic or aromatic hydrocarbon group. Preferably, L ⁶ represents an alkylene group, an alkenylene group, an alkynylene group or an arylene group. Further, L ⁶ may contain other functional groups that do not react with the isocyanate group, such as ether, carbonyl, ester, cyano, olefin, urethane, amide, ureido group or halogen atom. n3 is an integer of 2 or more, and preferably represents an integer of 2 to 100.

  Specific examples of the diol compound represented by the above formula (12), (13) or (14) include (Exemplary Compound No. 1) to (Exemplary Compound No. 18) shown below. N in the specific examples represents an integer of 2 or more.

  Moreover, in the synthesis | combination of specific polyurethane resin, the diol compound which has a substituent which does not react with an isocyanate group other than the said diol compound can also be used together. Examples of such diol compounds include those shown below.

In the formulas (15) and (16), L ⁷ and L ⁸ may be the same or different, and each may have a substituent (for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, -F,- And a divalent aliphatic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group which may have a halogen atom such as Cl, -Br and -I. If necessary, L ⁷ and L ⁸ may have another functional group that does not react with an isocyanate group, such as a carbonyl group, an ester group, a urethane group, an amide group, or a ureido group. Note that L ⁷ and L ⁸ may form a ring.

Furthermore, in the synthesis of the specific polyurethane resin, in addition to the diol compound, a diol compound having a carboxyl group can be used in combination.
Examples of such diol compounds include those represented by the following formulas (17) to (19).

In formulas (17) to (19), R ¹⁵ represents a hydrogen atom, a substituent (for example, a cyano group, a nitro group, a halogen atom such as —F, —Cl, —Br, —I, etc.), —CONH ₂ , —COOR ^16. , -OR ¹⁶ , -NHCONHR ¹⁶ , -NHCOOR ¹⁶ , -NHCOR ¹⁶ , -OCONHR ¹⁶ (wherein R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms and an aralkyl group having 7 to 15 carbon atoms). Represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group, which may have a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 6 to 6 carbon atoms. Represents 15 aryl groups. L ⁹ , L ¹⁰ , and L ¹¹ may be the same or different, and may have a single bond or a substituent (for example, alkyl, aralkyl, aryl, alkoxy, or halogeno groups are preferable). Represents a divalent aliphatic or aromatic hydrocarbon group, preferably an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms. . If necessary, L ^{9 to} L ¹¹ may have another functional group that does not react with an isocyanate group, such as a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, or an ether group. A ring may be formed by 2 or 3 of R ¹⁵ , L ⁷ , L ⁸ and L ⁹ .
Ar represents a trivalent aromatic hydrocarbon group which may have a substituent, and preferably represents an aromatic group having 6 to 15 carbon atoms.

Specific examples of the diol compound having a carboxyl group represented by the above formulas (17) to (19) include those shown below.
3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, Bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine N, N-bis (2-hydroxyethyl) -3-carboxy-propionamide and the like.

  The presence of such a carboxyl group is preferable because the polyurethane resin can be provided with characteristics such as hydrogen bonding properties and alkali solubility. More specifically, the polyurethane resin having an ethylenically unsaturated bond group in the side chain is a resin further having a carboxyl group in the side chain, and more specifically, an ethylenically unsaturated bond group in the side chain. A polyurethane resin having 0.3 meq / g or more and having a carboxyl group in the side chain of 0.4 meq / g or more is particularly preferably used as the binder polymer of the present invention.

  In addition to the diol, a compound obtained by ring-opening a tetracarboxylic dianhydride represented by the following formulas (20) to (22) with a diol compound may be used in combination with the synthesis of the specific polyurethane resin. it can.

In formulas (20) to (22), L ¹² may have a single bond or a substituent (for example, alkyl, aralkyl, aryl, alkoxy, halogeno, ester, or amide groups are preferred). Represents an aliphatic or aromatic hydrocarbon group, —CO—, —SO—, —SO ₂ —, —O— or S—, preferably a single bond and a divalent aliphatic carbon having 1 to 15 carbon atoms. hydrogen _{group, -CO -, - SO 2 -} , - represents O- or S- to. R ¹⁷ and R ¹⁸ may be the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or a halogeno group, preferably a hydrogen atom or an alkyl having 1 to 8 carbon atoms. Group, an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogeno group. Two of L ¹² , R ¹⁷ and R ¹⁸ may combine to form a ring.

R ¹⁹ and R ²⁰ may be the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a halogeno group, preferably a hydrogen atom, an alkyl having 1 to 8 carbon atoms, or a carbon number of 6 Represents ~ 15 aryl groups. Two of L ¹² , R ¹⁹ and R ²⁰ may be bonded to form a ring. L ¹³ and L ¹⁴ may be the same or different and each represents a single bond, a double bond, or a divalent aliphatic hydrocarbon group, preferably a single bond, a double bond, or a methylene group. A represents a mononuclear or polynuclear aromatic ring. Preferably, it represents an aromatic ring having 6 to 18 carbon atoms.

Specific examples of the compound represented by the above formula (20), (21) or (22) include those shown below.
That is, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4′-sulfonyldiphthalic dianhydride, 2,2-bis (3 , 4-Dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 4,4 ′-[3,3 ′-(alkylphosphoryldiphenylene) -bis (iminocarbonyl) ] Diphthalic dianhydride,

  Aromatic tetracarboxylic dianhydrides such as adducts of hydroquinone diacetate and trimetic anhydride, diacetyldiamine and trimetic anhydride; 5- (2,5-dioxotetrahydrofuryl) -3-methyl- 3-cyclohexsi-1,2-dicarboxylic anhydride (Dainippon Ink Chemical Co., Ltd., Epicron B-4400), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2 Alicyclic tetracarboxylic dianhydrides such as 1,4,5-cyclohexanetetracarboxylic dianhydride, tetrahydrofuran tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1, Aliphatic tetracarboxylic dianhydrides such as 2,4,5-pentanetetracarboxylic dianhydride may be mentioned.

Examples of a method for introducing a compound obtained by ring-opening these tetracarboxylic dianhydrides with a diol compound into a polyurethane resin include the following methods.
a) A method of reacting an alcohol-terminated compound obtained by ring-opening tetracarboxylic dianhydride with a diol compound and a diisocyanate compound.
b) A method of reacting an alcohol-terminated urethane compound obtained by reacting a diisocyanate compound under an excess of a diol compound with tetracarboxylic dianhydride.

Specific examples of the diol compound used for the ring-opening reaction include those shown below.
That is, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6-hexanediol, 2-butene- 1,4-diol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated Bisphenol F, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol F ethylene oxide adduct, bisphenol F pro Renoxide adduct, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfone, bis (2-hydroxyethyl) -2, Examples include 4-tolylene dicarbamate, 2,4-tolylene-bis (2-hydroxyethylcarbamide), bis (2-hydroxyethyl) -m-xylylenedicarbamate, and bis (2-hydroxyethyl) isophthalate.

  The specific polyurethane resin that can be used in the present invention is synthesized by adding the above-mentioned diisocyanate compound and diol compound to an aprotic solvent and adding a known catalyst having an activity corresponding to the respective reactivity, and heating. The molar ratio (Ma: Mb) of the diisocyanate and diol compound used in the synthesis is preferably 1: 1 to 1.2: 1, and desired physical properties such as molecular weight or viscosity by treating with alcohols or amines. Is finally synthesized in such a way that no isocyanate groups remain.

  As an introduction amount of the ethylenically unsaturated bond contained in the specific polyurethane resin according to the present invention, in terms of equivalent, 0.3 meq / g or more of an ethylenically unsaturated bond group in the side chain, and further 0.35 to It is preferable to contain 1.50 meq / g. Furthermore, a polyurethane resin containing a carboxyl group in the side chain of 0.4 meq / g or more, more preferably 0.45 to 1.00 meq / g together with an ethylenically unsaturated bond group is particularly preferable as the binder polymer of the present invention.

  The molecular weight of the specific polyurethane resin according to the present invention is preferably 5000 or more in terms of weight average molecular weight, and more preferably in the range of 10,000 to 100,000. In particular, when the photosensitive composition of the present invention is used for a color filter, the adhesion strength of the image area is excellent when the weight average molecular weight is within this range, and the developability of the non-image area by the alkaline developer is excellent.

  Moreover, what has an unsaturated group in a polymer terminal and a principal chain is also used suitably for the specific polyurethane resin which concerns on this invention. By having an unsaturated group at the polymer terminal and main chain, the crosslinking reactivity is further improved between the polymerizable compound and the specific polyurethane resin, or between the specific polyurethane resins, and the exposure sensitivity is increased. As a result, when the specific polyurethane resin is used for the color filter, a pixel having excellent adhesion strength can be provided. Here, as an unsaturated group, it is especially preferable to have a carbon-carbon double bond from the viewpoint of easy occurrence of a crosslinking reaction.

Examples of the method for introducing an unsaturated group at the polymer terminal include the following methods. That is, in the above-described process of synthesizing the polyurethane resin, in the step of treating with the residual isocyanate group at the polymer terminal and the alcohol or amine, an alcohol or amine having an unsaturated group may be used. Specific examples of such a compound include the same compounds as those exemplified above as the monofunctional alcohol or monofunctional amine compound having an unsaturated group.
The unsaturated group is preferably introduced into the polymer side chain rather than the polymer terminal from the viewpoint that the introduction amount can be easily controlled and the introduction amount can be increased, and that the crosslinking reaction efficiency is improved.

From the viewpoint of exposure sensitivity, the ethylenically unsaturated bond group to be introduced is preferably a methacryloyl group, an acryloyl group or a styryl group, more preferably a methacryloyl group or an acryloyl group. From the viewpoint of achieving both curability and storage stability of the photosensitive composition, a methacryloyl group is more preferable.
The amount of methacryloyl group introduced is preferably 0.30 meq / g or more, and more preferably in the range of 0.35 to 1.50 meq / g, as described above. That is, as the binder polymer of the present invention, a polyurethane resin in which a methacryloyl group is introduced into the side chain in a range of 0.35 to 1.50 meq / g is the most preferable embodiment.

As a method of introducing an unsaturated group into the main chain, there is a method of using a diol compound having an unsaturated group in the main chain direction for the synthesis of a polyurethane resin. Specific examples of the diol compound having an unsaturated group in the main chain direction include the following compounds.
That is, cis-2-butene-1,4-diol, trans-2-butene-1,4-diol, polybutadiene diol, and the like.

  The specific polyurethane resin according to the present invention can be used in combination with an alkali-soluble polymer containing a polyurethane resin having a structure different from that of the specific polyurethane resin. For example, the specific polyurethane resin can be used in combination with a polyurethane resin containing an aromatic group in the main chain and / or side chain.

  Next, the specific styrene resin, which is another preferred embodiment of the present invention, will be described in detail.

(Styrenic resin having an ethylenically unsaturated bond in the side chain)
The specific styrene resin used in the present invention includes, on its side chain, a styrenic double bond (styrene and α-methylstyrene double bond) represented by the following general formula (23), and the following general formula ( And those having at least one of the vinylpyridinium groups represented by 24).

In the general formula (23), R ²¹ represents a hydrogen atom or a methyl group. R ²² represents any substitutable atom or atomic group. k represents an integer of 0 to 4.
In addition, the styrenic double bond represented by the general formula (23) is connected to the polymer main chain through a single bond or a connecting group consisting of an arbitrary atom or atomic group, and the way of bonding is particularly There is no limit.
Although the preferable example is shown as a repeating unit of the high molecular compound which has a functional group represented by General formula (23) below, this invention is not limited to these examples.

In the general formula ^{(24), R 23} represents a hydrogen atom or a methyl group. R ²⁴ represents any substitutable atom or atomic group. m represents an integer of 0 to 4. A ^- represents an anion. Further, the pyridinium ring may take the form of benzopyridinium fused with a benzene ring as a substituent, and in this case includes a quinolium group and an isoquinolium group.
The vinylpyridinium group represented by the general formula (24) is connected to the polymer main chain through a single bond or a connecting group consisting of an arbitrary atom or atomic group, and there is no particular limitation on the way of bonding. Absent.
Although the preferable example is shown below as a repeating unit of the high molecular compound which has a functional group represented by General formula (24) below, this invention is not limited to these examples.

  One of the methods for synthesizing the specific styrene resin according to the present invention has a functional group represented by the general formula (23) or (24) and can be copolymerized with other copolymerization components. A method of copolymerizing monomers having functional groups using a known copolymerization method can be mentioned. Here, the specific styrene-based resin may be a homopolymer having only one of the functional groups represented by the general formulas (23) and (24), or either one of them, Alternatively, it may be a copolymer having two or more of both functional groups.

  Further, it may be a copolymer with other copolymerization monomers not containing these functional groups. As another copolymerization monomer in this case, it is preferable to select a carboxy group-containing monomer, for example, for the purpose of imparting solubility to an aqueous alkaline solution to the polymer. Acrylic acid, methacrylic acid, acrylic acid 2-carboxyethyl ester Examples thereof include 2-carboxyethyl methacrylate, crotonic acid, maleic acid, fumaric acid, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like.

  In addition to the monomer having a carboxy group, other monomer components may be introduced into the copolymer to be synthesized and used as a (multi-component) copolymer. In such cases, monomers that can be incorporated into the copolymer include styrene, 4-methylstyrene, 4-hydroxystyrene, 4-acetoxystyrene, 4-carboxystyrene, 4-aminostyrene, chloromethylstyrene, and 4-methoxystyrene. Styrene derivatives such as, vinylphosphonic acid, vinylsulfonic acid and salts thereof, styrenesulfonic acid and salts thereof, 4-vinylpyridine, 2-vinylpyridine, N-vinylimidazole, N-vinylcarbazole, 4-vinylbenzyltrimethylammonium chloride Quaternized product of N-vinylimidazole with methyl chloride, 4-vinylbenzylpyridinium chloride, acrylonitrile, methacrylonitrile, phenylmaleimide, hydroxyphenylmaleimide, vinyl acetate, Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate, vinyl ethers such as methyl vinyl ether, butyl vinyl ether, N-vinylpyrrolidone, acryloylmorpholine, vinyl chloride, vinylidene chloride, allyl alcohol Various monomers such as vinyltrimethoxysilane are appropriately used as copolymerization monomers.

  When using the above copolymer as the specific styrene resin according to the present invention, the copolymer has a functional group represented by the general formula (23) and / or the general formula (24) in the entire copolymer composition. The ratio of the repeating unit is preferably 20% by mass or more, and more preferably 40% by mass or more. Within this range, the effect of the present invention is excellent and a highly sensitive crosslinking system is provided.

In addition, the specific styrene resin according to the present invention may have water-soluble properties by including a quaternary salt structure in the repeating unit. In particular, a quaternary salt structure is formed in the linking group that has the functional group represented by the general formula (23) in the repeating unit and connects the main chain and the functional group represented by the general formula (23). When it has (for example, the specific examples P-6, P-23, and P-24, etc.), it may be a homopolymer having such a structure. It is preferable that it is a copolymer with the copolymerization monomer. For example, 4-vinylbenzyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, quaternized product of dimethylaminopropylacrylamide with methyl chloride, quaternized product of N-vinylimidazole with methyl chloride, 4- Vinylbenzylpyridinium chloride and the like are preferably used.
Further, in the case where the functional group represented by the general formula (24) is contained in the repeating unit, it may be a homopolymer or a copolymer with the above other copolymerization monomer. .

  Alternatively, when a carboxyl group is introduced as a copolymer, development with an alkaline aqueous solution is also possible. In any case, the proportion of the repeating unit having the functional group represented by the general formula (23) and / or the general formula (24) is preferably 20% by mass or more. Can be freely selected according to the purpose.

  The molecular weight of the specific styrene resin according to the present invention is preferably in the range of 5,000 to 300,000 in terms of weight average molecular weight, more preferably in the range of 10,000 to 100,000, and most preferably in the range of 20,000 to 150,000. . In particular, when the photosensitive composition of the present invention is used for a color filter, the adhesion strength of the image area is excellent when the weight average molecular weight is within this range, and the developability of the non-image area by the alkaline developer is excellent.

Next, the specific binder polymer (A) other than the specific polyurethane resin and the specific styrene resin will be described.
Examples of the novolak resin having an ethylenically unsaturated group in the side chain include, for example, a polymer described in JP-A-9-269596 and an ethylenically unsaturated group in the side chain by using the method described in JP-A-2002-62648. Examples thereof include a resin into which a saturated bond is introduced.
Examples of the acetal resin having an ethylenically unsaturated bond in the side chain include resins described in JP-A No. 2002-162741.
Examples of the polyamide-based resin having an ethylenically unsaturated bond in the side chain include the resin described in Japanese Patent Application No. 2003-321022, or the polyamide resin cited therein, as described in JP-A-2002-62648. Examples thereof include a resin in which an ethylenically unsaturated bond is introduced into the side chain.
Examples of the polyimide resin having an ethylenically unsaturated bond in the side chain include, for example, a resin described in Japanese Patent Application No. 2003-339785, or a polyimide resin cited therein, and a method described in JP-A-2002-62648. And a resin having an ethylenically unsaturated bond introduced in the side chain.

An alkali-soluble resin having a double bond in the side chain described in JP-A Nos. 2000-187322 and 2002-62698, and an amide group in the side chain described in JP-A No. 2001-242612 An alkali-soluble resin having an excellent balance of adhesion strength , sensitivity, and developability is preferable.

  As content of the binder polymer in a photosensitive composition, it is 1-50 mass% as solid content in a photosensitive composition, Preferably it is 3-40 mass%, More preferably, it is 5-25 mass%.

  The ratio of the polymerizable compound (A) and the binder polymer (B) of the present application can be used as long as (A) / (B) is 1.0 or less, preferably 0.01 or more and 1.0 or less. Yes, preferably from 0.1 to 0.9, more preferably from 0.3 to 0.85. When the ratio is larger than 1.0, the ratio of the polymerizable compound is increased and the side edges are likely to enter. On the other hand, if it is smaller than 0.01, the curability becomes low and the image formability becomes difficult.

<(C) Photopolymerization initiator>
The photosensitive composition of the present invention contains a photopolymerization initiator.
The photopolymerization initiator in the present invention is a compound that is decomposed by light and starts and accelerates the polymerization of the polymerizable compound (A), and preferably has an absorption in a wavelength region of 300 to 500 nm. Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

  Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaaryls. Examples include rubiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  Specific examples of organic halogenated compounds include Wakabayashi et al., “Bull. Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Examined Patent Publication No. 46-4605, JP-A 48-36281, JP-A 55-32070, JP-A 60-239736, JP-A 61-169835, JP-A 61-169837, JP-A 62-58241, JP 62-212401, JP-A 63-70243, JP-A 63-298339, M.S. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) , Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl methyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include mbenzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate, and the like.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaful Lophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

As the biimidazole compound, for example, a hexaarylbiimidazole compound (rophine dimer compound) is preferable.
Examples of the hexaarylbiimidazole compound include lophine dimers described in JP-B-45-37377 and JP-B-44-86516, JP-B-6-29285, U.S. Pat. No. 3,479,185, and the like. Various compounds described in each specification such as 4,311,783 and 4,622,286, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) vididazole, 2, 2'-bis (o , O′-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5 Examples include '-tetraphenylbiimidazole.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 In Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Japanese Patent Application Laid-Open No. 2000-66385, Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Application Publication No. 2004-534797 Compounds and the like.
Among oxime initiators, the following formula (3) is more preferable from the viewpoints of sensitivity, time stability, and coloring during post-heating.

In the general formula (vi), R and X ³ each independently represent a monovalent substituent, A ⁷ represents a divalent organic group, and Ar ⁰ represents an aryl group. n is an integer of 1-5.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. 18, 387 (1974), T .; S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. . In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  As the photopolymerization initiator (F) used in the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, phosphine Oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxa Compounds selected from the group consisting of diazole compounds and 3-aryl substituted coumarin compounds are preferred.

  More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo compounds. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

  In particular, when the photosensitive composition of the present invention is used for the production of a color filter of a solid-state imaging device, it is necessary to form fine pixels with a sharp shape, and therefore, a fine unexposed portion has a curable property. It is important to develop without residue. From such a viewpoint, an oxime compound is particularly preferable. In particular, when fine pixels are formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen contained in the photopolymerization initiator and the like. In view of these points, it is most preferable to use an oxime compound as a photopolymerization initiator (C) in order to form a finely colored pattern such as a solid-state imaging device. .

  The content of the (C) photopolymerization initiator contained in the photosensitive composition of the present invention is preferably 0.1 to 50% by mass, more preferably 0, based on the total solid content of the photosensitive composition. 0.5 to 30% by mass, particularly preferably 1 to 20% by mass. Within this range, good sensitivity and pattern formability can be obtained.

<(D) Titanium black dispersion>
The titanium black of the present invention is black particles having titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and can also be treated with a water repellent material as disclosed in JP-A-2007-302836. .

Further, the titanium black of the present invention is a black pigment such as a complex oxide such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline black, etc. for the purpose of adjusting dispersibility, colorability and the like. May be contained in one kind or a combination of two or more kinds. In this case, the titanium black particles occupy 50% by mass or more of the pigment.
In addition, for the purpose of controlling the light-shielding property of a desired wavelength, existing colorants such as red, blue, green, yellow, cyan, magenta, violet, orange, etc., or dyes, or carbon black, iron oxide It is also possible to add other black pigments such as manganese oxide and graphite.

  The pigment used in combination is preferably used in the range of 2 to 50 parts by mass, more preferably 2 to 30 parts by mass of the combined pigment, with respect to 100 parts by mass of the sum of the black pigment and the combined pigment. The combined pigment is preferably 2 to 10 parts by mass.

  Examples of commercially available titanium black products include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, Ako Kasei Co., Ltd., and Tilac D manufactured by Mitsubishi Materials Corporation.

  Titanium black is produced by heating a mixture of titanium dioxide and metal titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No. Sho 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), etc. is not.

The particle size of the titanium black particles is not particularly limited, but is preferably 3 to 2000 nm, more preferably 10 to 500 nm from the viewpoint of dispersibility and colorability.
The specific surface area of titanium black is not particularly limited, but the water repellency after surface treatment of such titanium black with a water repellent agent has a predetermined performance, and thus the value measured by the BET method is usually 5 to 150 m. ² / g approximately, it is preferably inter alia 20 to 100 m ² / g approximately.
Moreover, it is preferable to add a pigment dispersant from a viewpoint of improving the dispersibility of the above-mentioned titanium black.

Examples of pigment dispersants that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth) acrylates. , (Meth) acrylic copolymers, naphthalenesulfonic acid formalin condensates], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.
Moreover, the resin which has polymeric groups, such as an allyl group, a (meth) acryl group, and a styryl group, in a side chain can also be used suitably from a viewpoint of a sensitivity improvement for the dispersing agent used for this invention.
On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of the pigment dispersant that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010 ”manufactured by EFKA. 4165 (polyurethane series), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 ( Phthalocyanine derivatives), 6750 (a) Pigment derivatives) ”,“ Ajispur PB821, PB822 ”manufactured by Ajinomoto Fine Techno Co., Ltd.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd. “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Enomoto Kasei Co., Ltd., Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ Aceta Min 86 (stearylamine acetate), Lubrizol "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end) , 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical.

  These dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.

  As long as it can function as a solvent for dispersion, various water-soluble or water-insoluble solvents can be used, for example, water; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and allyl alcohol; Glycol or derivatives thereof such as ethylene glycol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol monoethyl ether, polypropylene glycol monoethyl ether, polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether; glycerol; Glycerol such as glycerol monoethyl ether and glycerol monoallyl ether Derivatives; ethers such as tetrahydrofuran and dioxane; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone; liquid paraffin, decane, decene, methyl naphthalene, decalin, kerosene, diphenylmethane, toluene, dimethylbenzene, Hydrocarbons such as ethylbenzene, diethylbenzene, propylbenzene, cyclohexane, partially hydrogenated triphenyl, polydimethylsiloxane, partially octyl-substituted polydimethylsiloxane, partially phenyl-substituted polydimethylsiloxane, silicone oils such as fluorosilicone oil, chlorobenzene , Halogenated hydrocarbons such as dichlorobenzene, bromobenzene, chlorodiphenyl, chlorodiphenylmethane, Kin Industries Co., Ltd.), demnum (Daikin Industries Co., Ltd.), fluorides, ethyl benzoate, octyl benzoate, dioctyl phthalate, trioctyl trimellitic acid, dibutyl sebacate, ethyl (meth) acrylate , Ester compounds such as butyl (meth) acrylate, dodecyl (meth) acrylate, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, N, N-dimethylacrylamide, N, N-dimethylacetamide, N An amide solvent such as methylpyrrolidone is appropriately selected and used alone or in combination.

  In preparing the titanium black dispersion according to the present invention, it is preferable to add 5 to 200 parts by mass, more preferably 10 to 100 parts by mass of the dispersant component with respect to 100 parts by mass of titanium black. That is, if the polymer is less than 5 parts by mass, it may be difficult to sufficiently modify the surface properties of titanium black. This is because the amount increases and there is a risk of impairing the inherently required characteristics of titanium black, such as light-shielding properties and coloring properties.

The content of the titanium black dispersion added to the photosensitive composition is adjusted such that the content in terms of solid content of titanium black in the photosensitive composition is 50% by mass or more and 90% by mass or less. The content of titanium black in the photosensitive composition is more preferably in the range of 25% by mass to 95% by mass, and still more preferably in the range of 40% by mass to 85% by mass.
By setting it as the said range, the sclerosis | hardenability of the photosensitive composition does not fall, and a uniform film | membrane can be formed. Further, since titanium black is contained at a high concentration, sufficient light shielding properties can be obtained, and a photosensitive composition containing the titanium black dispersion can be suitably used for forming a light shielding color filter.
The preferable transmittance exhibited by the light-shielding color filter of the present invention is 5% or less in the wavelength region of 800 to 1200 nm, and more preferably 3% or less and 1% or less.

-Photosensitive composition-
The photosensitive composition may further contain optional components described in detail below, if necessary.
Hereinafter, optional components that the photosensitive composition may contain will be described.

[Sensitizer]
The photosensitive composition may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength.
As the sensitizer that can be used in the present invention, a sensitizer that sensitizes the above-described (C) photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism is preferable.

Examples of the sensitizer used in the photosensitive composition include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
That is, for example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), Thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, Toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squaryu (Eg, squalium), acridine orange, coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes Carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, etc. Examples include aromatic ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

  As a sensitizer in the photosensitive composition of the present invention, more preferred examples include compounds represented by the following general formulas (e-1) to (e-4).

(In formula (e-1), B ¹ represents a sulfur atom or NR ⁷⁰ , R ⁷⁰ represents an alkyl group or an aryl group, and D ¹ represents the basicity of the dye in combination with adjacent B ¹ and the adjacent carbon atom. Represents a nonmetallic atomic group forming a nucleus, R ⁷¹ and R ⁷² each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁷¹ and R ⁷² are bonded to each other to form an acidic nucleus of the dye W may represent an oxygen atom or a sulfur atom.)

(In Formula (e-2), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —D ² —, where D ² represents —O— or —S—. In addition, W is synonymous with that shown in Formula (e-1).)

(In the formula (e-3), B ² represents a sulfur atom or NR ⁶⁹ , D ³ represents a nonmetallic atomic group that forms a basic nucleus of the dye in combination with adjacent B ² and a carbon atom, and R 3 ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ and R ⁶⁸ each independently represents a monovalent non-metallic atomic group, and R ⁶⁹ represents an alkyl group or an aryl group.)

(In Formula (e-4), B ³ and B ⁴ each independently represent —S— or —NR ⁶² , R ⁶² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and D ⁴ and D ⁵ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent B ³ and B ⁴ and adjacent carbon atoms, and R ⁶⁰ and R ⁶¹ each independently represent a monovalent group. And can be bonded to each other to form an aliphatic or aromatic ring.)

The content of the sensitizer in the photosensitive composition is preferably 0.1 to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency into the deep part and initiation decomposition efficiency, and preferably 0.5 to 15 mass% is more preferable.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

Further, as a preferable sensitizer that can be contained in the photosensitive composition, in addition to the above sensitizer, a compound represented by the following general formula (II) and a compound represented by the following general formula (III) are selected. At least one kind.
These may be used individually by 1 type, and may use 2 or more types together.

In the general formula (II), R ⁸¹ and R ⁸² each independently represent a monovalent substituent, and R ⁸³ , R ⁸⁴ , R ⁸⁵ and R ⁸⁶ each independently represent a hydrogen atom or a monovalent substituent. To express. m2 represents an integer of 0 to 5, m3 represents an integer of 0 to 5, and neither m2 nor m3 is 0. When m2 is 2 or more, a plurality of R ⁸¹ may be the same or different. When m3 is 2 or more, a plurality of R ⁸² may be the same or different. In the general formula (II), the isomer by the double bond is not limited to either.

The compound represented by the general formula (II) preferably has a molar extinction coefficient ε at a wavelength of 365 nm of 500 mol ⁻¹ · L · cm ⁻¹ or more, and ε at a wavelength of 365 nm of 3000 mol ⁻¹ · L · cm ^{−. 1} or more is more preferable, and ε at a wavelength of 365 nm is most preferably 20000 mol ⁻¹ · L · cm ⁻¹ or more. It is preferable that the value of the molar extinction coefficient ε at each wavelength is in the above range because the sensitivity improvement effect is high from the viewpoint of light absorption efficiency.

Although the preferable specific example of a compound represented by general formula (II) is illustrated below, this invention is not limited to these.
Note that in this specification, a chemical formula may be described by a simplified structural formula, and a solid line or the like that does not clearly indicate an element or a substituent particularly represents a hydrocarbon group.

In General Formula (III), B ⁵ represents an aromatic ring or a hetero ring that may have a substituent, X ² represents an oxygen atom, a sulfur atom, or —N (R ⁸⁹ ) —, and Y ⁵ represents An oxygen atom, a sulfur atom, or -N ( ^R89 )-is represented. R ⁸⁷ , R ⁸⁸ , and R ⁸⁹ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and B ⁵ , R ⁸⁷ , R ⁸⁸ , and R ⁸⁹ are each bonded to each other to form an aliphatic group Or aromatic rings may be formed.

In the general formula (III), R ⁸⁷ , R ⁸⁸ and R ⁸⁹ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group. When R ⁸⁷ , R ⁸⁸ and R ⁸⁹ represent a monovalent nonmetallic atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group It is preferably a heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

In the compound represented by the general formula (III), Y ⁵ is preferably an oxygen atom or —N (R ⁸⁹ ) — from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator. R ⁸⁹ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group. Further, Y ⁵ is most preferably —N (R ⁸⁹ ) —.

  Hereinafter, although the preferable specific example of a compound represented by general formula (III) is shown, this invention is not limited to this. Further, it is not clear about an isomer by a double bond connecting an acidic nucleus and a basic nucleus, and the present invention is not limited to either isomer.

[Co-sensitizer]
It is preferable that the photosensitive composition further contains a co-sensitizer.
In the present invention, the co-sensitizer further enhances the sensitivity of (C) the photopolymerization initiator and the sensitizer to actinic radiation, or suppresses the polymerization inhibition of (A) the polymerizable compound by oxygen. Have.

  Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these cosensitizers is in the range of 0.1 to 30% by mass with respect to the mass of the total solid content of the photosensitive composition from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and chain transfer. Preferably, the range of 1-25 mass% is more preferable, and the range of 0.5-20 mass% is still more preferable.

[Adhesion improver]
In the photosensitive composition, an adhesion improver can be added in order to improve adhesion to a hard surface such as a support. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is most preferable.

  0.1-30 mass% is preferable in the total solid of a photosensitive composition, and, as for the addition amount of an adhesive improvement agent, 0.5-20 mass% is more preferable.

[Diluent]
The photosensitive composition may use various organic solvents as a diluent.
The organic solvent used here is acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like.
These solvents can be used alone or in combination. The concentration of the solid content with respect to the organic solvent is preferably 2 to 60% by mass.

<Thermal polymerization inhibitor>
In the present invention, a small amount of a thermal polymerization inhibitor may be added in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the photosensitive composition. desirable.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

  The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the solid content of the photosensitive composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

[Other additives]
Furthermore, in order to improve the physical properties of the cured film, a known additive such as an inorganic filler or a plasticizer may be added to the photosensitive composition.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. , 10% by mass or less can be added with respect to the total mass of the polymerizable compound and the binder polymer.

<Color filter and manufacturing method thereof>
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of the present invention is characterized by having a colored pattern formed on the support using the photosensitive composition for a color filter of the present invention.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

In the present invention, the “light-shielding color filter” refers to a light-shielding material obtained by exposing and developing a photosensitive composition containing at least a black color material containing titanium black, a polymerizable compound, a binder polymer, and a photopolymerization initiator. Refers to the sex pattern. The color of the “light-shielding color filter” in the present invention may be an achromatic color such as black or gray, or a black or gray color mixed with a chromatic color.
The “light-shielding color filter” is obtained by exposing and developing a photosensitive composition containing at least a black color material containing titanium black, a polymerizable compound, a binder polymer, and a photopolymerization initiator. In other words, the light shielding film or the light shielding filter.

  The method for producing a color filter of the present invention is a process of forming a photosensitive composition layer by applying the photosensitive composition of the present invention on a support (hereinafter referred to as “photosensitive composition layer forming process” as appropriate). And a step of exposing the photosensitive composition layer through a mask (hereinafter abbreviated as “exposure step” where appropriate), and developing the photosensitive composition layer after exposure to form a colored pattern. And a forming step (hereinafter, abbreviated as “development step” as appropriate).

Specifically, the photosensitive composition of the present invention is applied directly or via another layer onto a support (substrate) to form a photosensitive composition layer (photosensitive composition layer forming step). Then, it is exposed through a predetermined mask pattern, only the coating film portion irradiated with light is cured (exposure process), and developed with a developer (development process) to form a pattern film composed of pixels of each color. The color filter of the present invention can be manufactured.
Hereinafter, each process in the manufacturing method of the color filter of this invention is demonstrated.

[Photosensitive composition layer forming step]
In the photosensitive composition layer forming step, the photosensitive composition of the present invention is applied on a support to form a photosensitive composition layer.

As the support that can be used in this step, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these glasses, imaging elements, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  As a coating method of the photosensitive composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied.

As a coating film thickness (film thickness after drying) of the photosensitive composition, 0.1 μm to 10 μm is preferable, 0.2 μm to 5 μm is more preferable, and 0.2 μm to 3 μm is still more preferable.
Moreover, when manufacturing the color filter for solid-state image sensors, as a coating film thickness (film thickness after drying) of a photosensitive composition, it is 0.35 micrometer-1.5 micrometers from a viewpoint of resolution and developability. Preferably, 0.40 μm to 1.0 μm is more preferable.

  The photosensitive composition coated on the support is usually dried at 70 ° C. to 130 ° C. for about 1 minute to 5 minutes to form a photosensitive composition layer.

[Exposure process]
In the exposure step, the photosensitive composition layer formed in the photosensitive composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is more preferably ^5mJ / cm ^{2 ~2000mJ} / cm 2 is preferably ^{10mJ / cm 2 ~1000mJ / cm 2} , 10mJ / cm 2 ~800mJ / cm 2 being most preferred.

[Development process]
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part remains.
As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

  As the alkali used in the developer, for example, an inorganic developer such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metaoxalate, etc. can be used, preferably aqueous ammonia, In an aqueous solution of an organic alkaline compound such as ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is there. An alkaline aqueous solution diluted with pure water is used so that the alkali concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  In addition, in the manufacturing method of the color filter of this invention, after performing the photosensitive composition layer formation process, the exposure process, and the image development process which were mentioned above, the formed colored pattern is heated and / or exposed as needed. A curing step for curing may be included.

  By repeating the photosensitive composition layer forming step, the exposure step, and the development step (and, if necessary, the curing step) described above for the desired number of hues, a color filter having a desired hue is produced.

Since the color filter of the present invention uses the photosensitive composition of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition is excellent in development resistance. It is possible to form a high-resolution pattern that is excellent in sensitivity, has good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape. Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. That is, the color filter of the present invention is preferably applied to a solid-state image sensor.
The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

<Solid-state imaging device>
The solid-state image sensor according to the present invention includes the light-shielding color filter for the solid-state image sensor according to the present invention described above.
Since the solid-state image sensor of the present invention is equipped with the light-shielding color filter for the solid-state image sensor of the present invention in which a decrease in light shielding ability in the peripheral portion is suppressed, noise can be reduced and color reproducibility can be improved. Can be made.
The configuration of the solid-state imaging device of the present invention is a configuration provided with the light-shielding color filter for the solid-state imaging device of the present invention, and is not particularly limited as long as the configuration functions as a solid-state imaging device. A light receiving element comprising a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) is provided on the opposite side of the light receiving element forming surface of the support. The structure with which the light-shielding color filter for solid-state image sensors of this invention was provided in the surface is mentioned.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

(Synthesis of specific resin 1)
Put 800 parts of cyclohexanone in a reaction vessel, heat to 100 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 60.0 parts of styrene, 80.0 parts of methacrylic acid, 68.0 parts of methyl methacrylate, butyl methacrylate A mixture of 62.0 parts and 11.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to conduct a polymerization reaction. After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, and then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain a weight average molecular weight. Of about 30000, 3.44 mmol / g of acrylic resin 1 was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. A solution of the specific resin 1 was prepared.

(Synthesis of specific resin 2)
1070 parts of the acrylic resin 1 solution, 10 parts of glycidyl methacrylate and 1 part of tetraethylammonium bromide were added and stirred at 90 ° C. for 2 hours to obtain a specific resin 2 in which a double bond group was introduced into the side chain.
The weight average molecular weight was about 32000, and the acid amount was 3.1 mmol / g.
The amount of solvent was adjusted to 20% by mass.

(Synthesis of specific resin 3)
334 parts of a 30% by mass propylene glycol monomethyl ether acetate solution of polyacrylic acid / methyl methacrylate (mass ratio 50 parts by mass / 50 parts by mass) having a weight average molecular weight of 10,000 and an acid amount of 6.9 mmol / g and 50 of glycidyl methacrylate Part and tetraethylammonium bromide 1 part were added, and it stirred at 90 degreeC for 3 hours, and obtained the specific resin 3 which introduce | transduced the double bond group into the side chain.
A resin having a weight average molecular weight of 12000 and an acid amount of 1.95 mmol / g was obtained, the amount of solvent was adjusted, and the solid content was 20% by mass.

(Synthesis of specific resin 4)
In a 1000 ml three-necked flask, 100 g of 1-methyl-2-pyrrolidone was added and heated to 90 ° C. under a nitrogen stream. To this, 100 g of 1-methyl-2-pyrrolidone solution of 84 g of the following compound (i-1), 33 g of benzyl methacrylate, 14 g of methacrylic acid, and 5.2 g of V-601 (azo initiator manufactured by Wako Pure Chemical Industries, Ltd.) It was added dropwise over time. After completion of dropping, the mixture was further stirred for 2 hours. Thereafter, the reaction solution was cooled to room temperature and then poured into 7 L of water to precipitate a polymer compound. The precipitated polymer compound was collected by filtration, washed with water and dried to obtain 131 g of a polymer compound.
It was 11800 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance. The acid value of this polymer compound was determined by titration and found to be 69.6 mgKOH / g (calculated value 69.7 mgKOH / g).

  As described above, 131 g of the polymer compound obtained in the 1000 ml three-necked flask was added with 1.0 g of p-methoxyphenol, further dissolved with 580 g of 1-methyl-2-pyrrolidone, and an ice bath containing ice water. It was cooled with. After the temperature of the mixed solution became 5 ° C. or lower, 150 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) was further added dropwise over 1 hour using a dropping funnel. After completion of dropping, the ice bath was removed and the mixture was further stirred for 8 hours. The obtained reaction solution was adjusted to pH 7 by adding concentrated hydrochloric acid, and then poured into 7 L of water to precipitate a polymer compound [specific resin (I)]. The precipitated polymer compound was collected by filtration, washed with water and dried to obtain 105 g of the intended specific resin 4.

(Synthesis of specific resin 5)
In a 500 ml three-necked round bottom flask equipped with a condenser and a stirrer, 8.2 g (0.05 mol) of 2,2-bis (hydroxymethyl) butanoic acid, 8.01 g (0) of the following diol compound (0) .05 mol) was dissolved in 100 ml of N, N-dimethylacetamide. To this, 25.5 g (0.102 mol) of 4,4-diphenylmethane diisocyanate and 0.1 g of dibutyltin dilaurate were added, and the mixture was heated and stirred at 100 ° C. for 6 hours to carry out urethane polymerization. Thereafter, the mixture was diluted with 100 ml of N, N-dimethylformamide and 200 ml of methyl alcohol and stirred for 30 minutes. The reaction solution was poured into 3 liters of water with stirring to precipitate a white polymer. This polymer was separated by filtration, washed with water, and dried under vacuum to obtain 37 g of polymer (specific resin 5).
When the molecular weight was measured by gel permeation chromatography (GPC), the weight average molecular weight (polystyrene standard) was 60,000.

Specific resin 6 benzyl methacrylate / methacrylic acid 7/3 mol ratio
Weight average molecular weight 30,000 Acid amount 2.01 mmol / g

(Preparation of photosensitive composition)
<Preparation of Titanium Black Dispersion A>
The following composition 1 was subjected to a high viscosity dispersion treatment with two rolls to obtain a dispersion. The viscosity of the dispersion at this time was 40,000 mPa · s.
In addition, you may knead | mix for 30 minutes with a kneader before a high-viscosity dispersion process.

<Composition 1>
-Average primary particle size 75 nm Titanium black 13M-C 40 parts (Mitsubishi Materials Corporation) (Pigment Black 35)
8 parts of a benzyl methacrylate / methacrylic acid copolymer propylene glycol monomethyl ether acetate solution (BzMA / MAA = 72/28 mol ratio, Mw: 28000, solid content 40% by mass)
・ 2 parts of Solsperse 5000 (manufactured by Zeneca)

The following composition 2 was added to the obtained dispersion, and the mixture was stirred for 3 hours using a homogenizer at 3000 rpm. The obtained mixed solution was subjected to fine dispersion treatment for 4 hours with a disperser (trade name: manufactured by Dispermat GETZMANN) using 0.3 mm zirconia beads, and titanium black dispersion A (hereinafter referred to as TB dispersion). A.) was obtained.
At this time, the viscosity of the mixed solution was 7.0 mPa · s.

<Composition 2>
10 parts of a benzyl methacrylate / methacrylic acid copolymer propylene glycol monomethyl ether acetate solution (BzMA / MAA = 70/30 mol ratio, Mw: 30000, solid content: 40% by mass)
・ 200 parts of propylene glycol monomethyl ether acetate

<Preparation of titanium black dispersion B>
The following composition 3 was subjected to a high viscosity dispersion treatment with two rolls to obtain a dispersion. The viscosity of the dispersion at this time was 40,000 mPa · s.
In addition, you may knead | mix for 30 minutes with a kneader before a high-viscosity dispersion process.

<Composition 3>
-Average primary particle size 75nm Titanium black 13M-C 39 parts (Mitsubishi Materials Corporation) (Pigment Black 35)
8 parts of propylene glycol monomethyl ether acetate solution of allyl methacrylate / methyl methacrylate / methacrylic acid copolymer (allyl methacrylate / methyl methacrylate / methacrylic acid = 50/20/30 mol ratio, Mw: 26000, solid content 40% by mass)
・ 1 part of Solsperse 5000 (Zeneca)

The following component 4 was added to the obtained dispersion, and the mixture was stirred for 3 hours using a homogenizer at 3000 rpm. The obtained mixed solution was subjected to fine dispersion treatment for 4 hours with a disperser (trade name: manufactured by Dispermat GETZMANN) using 0.3 mm zirconia beads to obtain titanium black dispersion B (hereinafter referred to as TB dispersion). B).
At this time, the viscosity of the mixed solution was 7.0 mPa · s.

<Composition 4>
8 parts of propylene glycol monomethyl ether acetate solution of allyl methacrylate / methacrylic acid copolymer (allyl methacrylate / methacrylic acid = 70/30 mol ratio, Mw: 25000, solid content 40% by mass)
・ 200 parts of propylene glycol monomethyl ether acetate

<Preparation of carbon black dispersion A>
The following composition 5 was subjected to high viscosity dispersion treatment with two rolls to obtain a dispersion. The viscosity of the dispersion at this time was 70000 mPa · s.
Then, the following composition 6 was added to this dispersion, and it stirred for 3 hours using the homogenizer on 3000 rpm conditions. The obtained mixed solution was subjected to a fine dispersion treatment for 4 hours with a disperser (trade name: manufactured by Dispermat GETZMANN) using 0.3 mm zirconia beads to obtain a carbon black dispersion A (hereinafter referred to as CB dispersion A). Was written). At this time, the viscosity of the mixed solution was 37 mPa · s.

<Composition 5>
-Average primary particle size 15 nm carbon black (Pigment Black 7) 23 parts-Benzyl methacrylate / methacrylic acid copolymer propylene glycol monomethyl ether acetate 45% solution 22 parts (benzyl methacrylate / methacrylic acid = 67/33 mol ratio, Mw: 28000)
・ Solsperse 5000 (manufactured by Zeneca) 1.2 parts

<Composition 6>
22 parts of a 45% propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid copolymer (benzyl methacrylate / methacrylic acid = 67/33 mol ratio, Mw: 28000)
・ 200 parts of propylene glycol monomethyl ether acetate

<Adjustment of black photosensitive composition>
Components of the following composition A were mixed with a stirrer to prepare a black photosensitive composition.
(Composition A)
-Binder: Specific resin numbers and parts by mass are listed in Table 1. (Parts indicate solid content.)
Polymerizable compound: The compounds used and the parts by mass are listed in Table 1.
-Dispersion: listed in Table 1-24 parts-propylene glycol monomethyl ether acetate-18 parts-photopolymerization initiator: compounds listed in Table 1 (structures are listed in Table 2) 0.7 parts-thermal polymerization inhibitor (p- Methoxyphenol) 0.001 part

[Production of silicon wafer with undercoat layer]
Components of the following resist composition were mixed and dissolved to prepare a resist solution for the undercoat layer.
<Resist composition>
Propylene glycol monomethyl ether acetate (PGMEA) 19.20 parts Ethyl lactate 36.67 parts Binder polymer 30.51 parts (benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60 / 22/18) 40% PGMEA solution)
Polymerizable compound: dipentaerythritol hexaacrylate 12.20 parts Polymerization inhibitor: p-methoxyphenol 0.0061 parts Fluorosurfactant 0.83 parts (F-475, Dainippon Ink & Chemicals, Inc.) Made)
-Photopolymerization initiator 0.586 parts (TAZ-107 (trihalomethyltriazine photopolymerization initiator, manufactured by Midori Chemical Co., Ltd.)

  A 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so as to have a dry film thickness of 2 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer, thereby obtaining a silicon wafer substrate with an undercoat layer. It was.

<Production of light-shielding color filter for solid-state imaging device and evaluation of sensitivity>
The photosensitive composition obtained above was applied to the silicon wafer with an undercoat layer obtained above by a spin coating method, and then heated at 120 ° C. for 2 minutes on a hot plate to obtain a photosensitive layer.
Then, the resulting light-sensitive layer, using an i-line stepper, the exposure amount in the range of exposure amount 100~5000mJ / cm ² through a photomask having a pattern of 3mm square, changes in steps of 100 mJ / cm ² And irradiated.
The photosensitive layer after the exposure was subjected to paddle development at 25 ° C. for 40 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide. Thereafter, it was rinsed with a spin shower and further washed with pure water to obtain a light-shielding color filter pattern. The minimum exposure amount at which a 3 mm square pattern was obtained after 60 seconds of development was shown.
From the viewpoint of productivity, 600 mJ / cm ² or less is favorable.

<Side edge evaluation>
Furthermore, about the side edge of Examples 1-14 of the black photosensitive composition obtained as mentioned above, it evaluated by the following method. The results are summarized in Tables 1 and 3.
That is, in the exposure process in the sensitivity evaluation, a 3 mm line is created and developed at 1000 mJ / cm ² , the pattern cross section is observed with a scanning electron microscope (SEM) image, and the vicinity of the substrate, the image surface layer portion, The difference in line width was measured.
A measurement width of 20 μm or less is good.

The compounds used in Examples and Comparative Examples in Table 1 and Table 3 are as follows.
MM-1: Dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.)
MM-2: Pentaerythritol tetraacrylate (NK ester A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.)
MM-3: Pentaerythritol triacrylate (NK ester A-TMPT manufactured by Shin-Nakamura Chemical Co., Ltd.)
MM-4: Glycerin PO-added triacrylate (Osaka Organic Chemical Co., Ltd. V # GPT)
MM-5: dimethylol dicyclopentane diacrylate (IRR214, manufactured by Daicel Ubicity)
MM-6: Pentaerythritol ethoxytetraacrylate (Ebecryl 40 manufactured by Daicel Ubicity)
MM-7: Tris (2-hydroxyethyl) isocyanurate triacrylate (SR-368, manufactured by Nippon Kayaku Co., Ltd.)
MM-8: Penaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (UA-306H manufactured by Kyoeisha Chemical Co., Ltd.)
MM-9: Succinic acid modified product of pentaerythritol triacrylate

Furthermore, the experiment was also performed with the following composition B in which the pigment concentration was increased. Evaluation was performed in the same manner as in Example 1, and the results are summarized in Table 3.
(Composition B)
-Binder: Specific resin numbers and parts by mass are listed in Table 3. (Parts indicate solid content.)
Polymerizable compound: Table 3 shows compounds used and parts by mass.
-Dispersion: listed in Table 3-24 parts-propylene glycol monomethyl ether acetate 10 parts-cyclohexanone 8 parts-photopolymerization initiator: compounds listed in Table 3 (structure is listed in Table 2) 0.8 parts-adhesion improver : 0.1 part below (S)

  From Table 1 and Table 3, the light-shielding color filter of the black solid-state imaging device using the titanium black dispersion of the present invention can be patterned with a low exposure amount, and has a small side edge and good pattern moldability. I understand that. In particular, Table 3 shows that the pattern formability is good even when the pigment concentration is increased to increase the shielding effect.

(Example 2-1)
<Production of solid-state image sensor>
-Preparation of chromatic coloring polymerizable composition-
In the preparation of TB dispersion A used in Example 15, in the same manner except that titanium black, which is a black pigment, was replaced with the following chromatic pigment, colored polymerizable composition R-1 for red (R), A colored polymerizable composition G-1 for green (G) and a colored polymerizable composition B-1 for blue (B) were prepared.

Chromatic pigment for forming colored pixels for each color of RGB, pigment for red (R) C.I. I. Pigment Red 254
-Green (G) pigment C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 219 30/70 [mass ratio] mixture and blue (B) pigment C.I. I. Pigment Blue 15: 6 and C.I. I. 30/70 [mass ratio] mixture with pigment violet 23

-Fabrication of color filters for solid-state image sensors-
The method described in Example 2-1 using the black photosensitive composition prepared in Example 15 as a black matrix, and using the colored polymerizable composition R-1 for red (R) on the black matrix. In the same manner as above, a red (R) coloring pattern of 1.6 × 1.6 μm was formed. Further, using the colored polymerizable composition G-1 for green (G) in the same manner, the colored polymerizable composition B-1 for green (G) and blue (B) of 1.6 × 1.6 μm was used. A blue (B) chromatic coloring pattern was sequentially formed to produce a color filter for a solid-state imaging device.

-Evaluation-
When a full-color color filter was incorporated in a solid-state imaging device, it was confirmed that the solid-state imaging device has a high light-shielding property of the light-shielding color filter, high resolution, low noise, and excellent color separation.

Claims (7)

  (A) polymerizable compound, (B) binder polymer, (C) photopolymerization initiator, and (D) titanium black dispersion, and (A) polymerizable compound / (B) binder polymer has a mass ratio of 1 A photosensitive composition which is 0.0 or less.   The photosensitive composition according to claim 1, wherein the (C) photopolymerization initiator is an oxime compound.   The photosensitive composition according to claim 1, wherein the (B) binder polymer is a compound having a polymerizable group in a side chain.   The photosensitive composition according to any one of claims 1 to 3, wherein a content of the titanium black is in a range of 40 to 85 mass% with respect to a total solid content of the photosensitive composition.   The photosensitive composition of any one of Claims 1-4 used for colored pattern formation in a solid-state image sensor.   The light-shielding color filter for solid-state image sensors which has a coloring pattern which uses the photosensitive composition of Claim 5 on a support body.   The solid-state image sensor provided with the light-shielding color filter for solid-state image sensors of Claim 6.