JP2013054079A - Photocurable composition, color filter, manufacturing method of the same, and solid imaging element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a photocurable composition which has high curing property, excellent uncured part removing property, and favorable pattern formation property during alkaline development, and is capable of forming a coloring region of excellent adhesion with a supporter; a color filter using the photocurable composition; a method of manufacturing the color filter; and a solid imaging element provided with the color filter.SOLUTION: The photocurable composition contains a radical polymerizable compound represented by general formula (1) and a photopolymerization initiator. The color filter using the photocurable composition, the method of manufacturing the color filter, and the solid imaging element provided with the color filter are also provided. (In general formula (1), a plurality of Rindependently represent a hydrogen atom or a methyl group, a plurality of R, R, and Rrespectively and independently represent a hydrogen atom or an organic group, a plurality of X independently represent an oxygen atom or a sulfur atom, Y represents an n-valent organic coupling group, and n represents an integer of 2 or more and 11 or less.)

Description

  The present invention relates to a photocurable composition, a color filter, a manufacturing method thereof, and a solid-state imaging device.

  Examples of the photocurable composition include those obtained by adding a photopolymerization initiator to a monomer having an ethylenically unsaturated bond. Since such a photocurable composition is polymerized and cured when irradiated with light, it is used in photocurable inks, photosensitive printing plates, color filters, various photoresists, and the like.

For example, in forming a color filter for LED, a pigment resist having only dipentaerythritol hexaacrylate (hereinafter abbreviated as DPHA) as a monomer has been used (see, for example, Patent Document 1). However, when only DPHA is used, a pigment resist to be removed by an alkaline developer during development sometimes remains on the substrate as a residue.
Thus, it has been proposed to use a carboxyl group-containing polyfunctional monomer in place of DPHA (see, for example, Patent Document 2), but the required performance has been further increased as follows.

A color filter for an image sensor has a pixel size of about 5 μm in the late 1990s due to a demand for improving the resolution of a solid-state imaging device such as a CCD. It is about to get smaller.
As the pixels became smaller, the contact area of the unexposed area with the alkaline developer decreased, resulting in the generation of residues due to poor dissolution and the tapering of the pattern shape. Due to the occurrence of residue, the sensitivity of adjacent pixels decreases, and due to increased taper, color mixing with adjacent pixels and gaps between pixels occur, resulting in increased noise and noticeable roughness in the reproduced image of the solid-state imaging device. There is a problem that the image quality tends to be impaired.
In particular, when a fine pixel pattern of 2.5 μm or less is formed, the generation of a residue due to poor solubility in the unexposed area was significant.
In addition, in recent years, there is a strong demand for high color density and thin film of color filters in order to improve image quality due to high light-condensing property and high color separation of a solid-state imaging device such as a CCD. When a large amount of coloring material was added to obtain a high coloring density, the alkali developability further deteriorated and the removability of unexposed areas was insufficient.

Patent Document 3 discloses a (meth) acrylic monomer compound having an amide methylol structure portion composed of —CO—NH—CH ₂ —O— as a polymerizable compound capable of suppressing volume shrinkage that occurs during photocuring. Yes.
As described above, while there is a strong demand for high color density and thinning of the color filter, the photocurable composition used for the production of the color filter is formed with good curability and developability. About a pattern, it has been calculated | required that adhesiveness with a support body is favorable and a shape is favorable.

JP-A-8-271723 Japanese Patent Laid-Open No. 10-332929 JP 2011-94089 A

The first object of the present invention has high curability, excellent removability of the uncured part at the time of alkali development, formed a good pattern without pattern wrinkles, and excellent adhesion to the support. It is providing the photocurable composition which can form a colored region.
Furthermore, a second object of the present invention is a color filter comprising the above-mentioned photocurable composition, having a good pattern shape, and having a colored pattern having excellent adhesion to a support, and the color Another object of the present invention is to provide a manufacturing method capable of manufacturing a filter with high productivity, and further to provide a solid-state imaging device including the color filter.

  Specific means for achieving the above object are as follows.

[1] A photocurable composition comprising (A) a radical polymerizable compound represented by the following general formula (1) and (B) a photopolymerization initiator.

[In General Formula (1), a plurality of R ₁ independently represent a hydrogen atom or a methyl group, and a plurality of R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or an organic group, X in the formula independently represents an oxygen atom or a sulfur atom, Y represents an n-valent organic linking group, and n represents an integer of 2 or more and 11 or less. ]

[2] The photocurable composition according to the above [1], wherein n in the general formula (1) is an integer of 3 or more and 7 or less.
[3] The photocurable composition according to the above [1] or [2], further comprising (C) a colorant.
[4] The photocurable composition according to [3], wherein the colorant (C) is a chromatic colorant.
[5] The photocurable composition according to [3], wherein the colorant (C) is a black colorant.
[6] The photocurable composition according to any one of [1] to [5] above, which contains an oxime-based photopolymerization initiator as a (B) photopolymerization initiator.
[7] In any one of the above [3] to [6], the content of (C) the colorant is 50% by mass or more and 90% by mass or less with respect to the total solid content of the photocurable composition. The photocurable composition as described.
[8] A step of applying the photocurable composition according to any one of [1] to [7] to form a photocurable composition layer, and using the photocurable composition layer as a mask The pattern formation method characterized by including the process to expose through and the process of developing the said photocurable composition layer after exposure.
[9] A color filter having a colored pattern formed using the photocurable composition according to any one of [3] to [7] on a support.
[10] A step of coating the photocurable composition according to any one of [3] to [7] on the support to form a photocurable composition layer, and the photocurable composition. A method for producing a color filter, comprising: exposing a physical layer through a mask; and developing the photocurable composition layer after exposure to form a colored pattern.
[11] A solid-state imaging device including the color filter according to [9].

According to the present invention, it cures with high sensitivity, and at the time of alkali development, forms a good pattern with excellent unremoved part removability, no pattern wrinkles, and excellent adhesion to the support. The photocurable composition which can be provided can be provided.
Furthermore, a color filter comprising the above-mentioned photocurable composition, having a good pattern shape and having a colored pattern having excellent adhesion to a support, and the color filter can be produced with high productivity. A manufacturing method, and further, a solid-state imaging device including the color filter can be provided.

<Photocurable composition>
The photocurable composition of the present invention comprises (A) a compound represented by the general formula (1) and (B) a photopolymerization initiator.
By using the compound represented by the general formula (1), it is possible to form a good pattern with excellent removability of the unexposed area and no pattern wrinkles.
The reason why the above effect can be obtained is not clear, but in particular, the excellent removability of the unexposed areas is that there are many such as dipentaerythritol hexaacrylate (DPHA) that has been suitably used for the production of color filters. It is surmised that the compound represented by the general formula (1) exhibits higher hydrophilicity than the functional monomer.
Hereinafter, the photocurable composition of the present invention will be described by taking a photocurable composition that can be suitably used for forming a color filter as an example, but the photocurable composition of the present invention is limited to these. is not.

-Photocurable composition-
<(A) Compound Represented by General Formula (1)>
The photocurable composition of the present invention contains (A) a compound represented by the general formula (1) (hereinafter, appropriately referred to as “specific polymerizable compound”).

In the general formula (1), a plurality of R _{1 s} independently represent a hydrogen atom or a methyl group, and a plurality of R ₂ , R _3, and R ₄ each independently represent a hydrogen atom or an organic group, X in the formula independently represents an oxygen atom or a sulfur atom, Y represents an n-valent organic linking group, and n represents an integer of 2 or more and 11 or less.

R ₂ , R ₃ and R ₄ in the general formula (1) represent a hydrogen atom or an organic group. Preferably it is a hydrogen atom.

Here, as the organic group of R ₂ , R ₃ , and R ₄ , a linear or branched, chain or cyclic alkyl group having 1 to 20 carbon atoms, a linear or branched chain having 2 to 20 carbon atoms, a chain or A hydrocarbon group such as a cyclic alkenyl group, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms (monocyclic or heterocyclic ring), or a combination of at least two of these, and These hydrocarbon groups are -C (= O) N-, -OC (= O) N-, -NC (= O) N-, -SC (= O) N-, -C (= S). -, -OC (= S)-, -NC (= S)-, -SC (= S)-, -O-, -C (= O) O-, -C (= O)-, -S- _{, -SO 2 -, - SO 3} -, - SO 2 N -, - NH -, - NR -, - NAr -, - N = N-, or, -N (= NH) N- (wherein, R Is an alkyl group, Alkenyl group, an alkynyl group, Ar is an aryl group (monocyclic, heterocyclic) represents a.) May comprise a divalent linking group, and the like.
As the organic group for R ₂ , R ₃ , and R ₄ , a methyl group is preferable.

R ₂ may form a ring with R ₃ and R ₄ via a linking group. As the linking group, an alkylene, a nitrogen atom, an oxygen atom, a benzene ring or the like can be appropriately combined. The number of ring members is preferably a 5- to 8-membered ring, more preferably a 5- to 6-membered ring.

  Moreover, in General formula (1), X represents an oxygen atom or a sulfur atom, Preferably it is an oxygen atom.

In general formula (1), Y represents an n-valent organic linking group that may have a substituent, and n represents an integer of 2 or more and 11 or less. Therefore, for example, when Y is divalent (n = 2), the general formula (1) is represented by the following general formula (1n = 2), and when A is trivalent (n = 3), the general formula (1) Is represented by the following general formula (1n = 3).
The n is preferably an integer of 3 or more and 7 or less from the viewpoint of improving sensitivity to light of the photocurable composition of the present invention.
When n is 1, the curability is low and a good pattern cannot be obtained.

In the general formula (1), the n-valent organic linking group represented by Y can be obtained by appropriately combining alkylene, a nitrogen atom, an oxygen atom, a benzene ring and the like so as to be n-valent. The organic linking group represented by Y is not particularly limited as long as it contains a carbon atom and is an n-valent linking group, but among them, the linking groups or substituents represented by the following a-1 to a-21 are appropriately combined. The n-valent linking group obtained above is preferable. The organic linking group represented by Y may be configured by combining not only one but also two or more of the following a-1 to a-21. In addition, the organic coupling group itself represented by the following a-1, a-3 to a-6, and a-8 to a-18 may be used.
The linking group as Y preferably has 3 to 3000 atoms, and more preferably 15 to 1000 atoms.

The linking group represented by Y preferably contains an alkylene oxide chain such as a-9 to a-14.
In the following, the n-valent organic linking group represented by Y is particularly preferably a structure represented by the following specific examples A-1 to A-25.

In said A-22, a is 1-30.
In said A-23, a is 1-30.
In said A-24, a is 1-30, b is 1-30, c is 1-30, d is 1-30.
In said A-25, a is 1-30, b is 1-30, c is 1-30, d is 1-30.

  Hereinafter, preferred specific examples of the specific polymerizable compound [compound represented by the general formula (1)] will be given, but the present invention is not limited thereto. In the following specific examples, a, b, c and d have the same meanings as a, b, c and d in the above (A-22), (A-23), (A-24) and (A-25). It is.

  The specific polymerizable compound (the compound represented by the general formula (1)) can be synthesized by, for example, a method represented by the following synthesis scheme, but is not limited to this method.

During the _{scheme, R 1, R 2, R} 3, R 4, X, Y, and n, _R 1 in the general formula _{(1), R 2, R} 3, R 4, X, Y, and n synonymous It is.

  A specific polymeric compound may be used individually by 1 type, and may use 2 or more types together.

  The specific polymerizable compound is preferably 0.5% by mass to 50% by mass and more preferably 3% by mass to 40% by mass with respect to the total solid mass of the photocurable composition of the present invention. preferable.

<Other photopolymerizable compounds>
The photocurable composition of the present invention may be used in combination with a photopolymerizable compound other than the specific polymerizable compound as long as the effects of the present invention are not impaired.
The addition amount of the photopolymerizable compound that may be used in combination other than the specific polymerizable compound is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, with respect to 100 parts by mass of the specific polymerizable compound.

  The photopolymerizable compound that may be used in combination is a compound other than the specific polymerizable compound, and a known photopolymerizable compound can be used. Specifically, it is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof. Photopolymerizable compounds other than the specific polymerizable compound may be used alone or in combination of two or more.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, 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 isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable 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 compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group as a polymerizable monomer and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates and the like, which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
As other preferable polymerizable compounds, compounds having a fluorene ring and having two or more functional ethylenic polymerizable groups described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and cardo resins. Can also be used.

  Further, compounds having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group are disclosed in paragraphs [0254] to [0257] of JP-A-2008-292970. The compounds described are also suitable.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the radical polymerizable monomers represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of Rs is —OC (═O) CH═CH ₂ , or represents an _{-OC (= O) C (CH} 3) = groups represented by CH _2.
Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraph numbers 0248 to 0251 of JP2007-26979A. Can also be suitably used in the present invention.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used as a polymerizable compound.

  Among them, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product: KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues. These oligomer types can also be used.

  As a polymeric compound, it is a polyfunctional monomer, Comprising: You may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture, it can be used as it is. However, if necessary, the hydroxyl group of the above-mentioned ethylenic compound is non-aromatic. An acid group may be introduced by reacting a group carboxylic anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  Further, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferred, and particularly preferred in this ester is that the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Alternatively, a part of the hydroxy group of the polyfunctional alcohol can be (meth) acrylated, and an acid anhydride is added to the remaining hydroxy group to form a carboxy group. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

  Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.

Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone structure as a polymeric compound.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, diester. Ε-caprolactone modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as pentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone Can be mentioned. Among these, a polyfunctional monomer having a caprolactone structure represented by the following formula (L) is preferable.

(In the formula, all six R are groups represented by the following formula (La), or 1 to 5 of the six R are groups represented by the following formula (La), The remainder is a group represented by the following formula (Lb).)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)
Such a polyfunctional monomer having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3)). , Number of groups represented by formula (2) = 2, compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (2) = 3 , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, compounds in which R ¹ is all hydrogen atoms), DPCA- 120 (a compound in which m = 2 in the formula, the number of groups represented by formula (2) = 6, and R ¹ is all hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

  Moreover, it is also preferable that it is at least 1 sort (s) selected from the group of the polymeric compound represented by the following general formula (i) or (ii).

In the general formulas (i) and (ii), each E independently represents — ((CH ₂ ) yCH ₂ O) — or — ((CH ₂ ) yCH (CH ₃ ) O) —, and y Each independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In said general formula (i), the sum total of acryloyl group and methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 0-40. However, when the total of each m is 0, any one of X is a carboxyl group.
In said general formula (ii), the sum total of acryloyl group and methacryloyl group is 5 or 6, n represents the integer of 0-10 each independently, and the sum total of each n is an integer of 0-60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In the general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (i) or formula (ii) in the _{- ((CH 2) yCH 2} O) - or _{- ((CH 2) yCH (} CH 3) O) - , the terminal oxygen atom side X The form which couple | bonds with is preferable.

  The compounds represented by the general formula (i) or (ii) may be used alone or in combination of two or more. In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.

  Moreover, as a total content in the specific monomer of the compound represented by general formula (i) or (ii), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

  The compound represented by the general formula (i) or (ii) is a ring-opening skeleton by a ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. And a step of reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton to introduce a (meth) acryloyl group. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formula (i) or (ii), a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

  Examples of commercially available compounds represented by the general formula (i) or (ii) include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and pentylene manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, Also suitable are urethane compounds having an ethylene oxide-based skeleton described in 58-49860, JP-B 56-17654, JP-B 62-39417, and JP-B 62-39418. Further, as polymerizable compounds, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are exemplified. By using it, it is possible to obtain a curable composition having an extremely excellent photosensitive speed.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

  About these polymerizable compounds, the details of the usage method 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 photocurable composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. In addition, from the viewpoint of increasing the strength of the cured film, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid esters, methacrylic acid esters, styrene compounds, vinyl ether compounds). A method of adjusting both sensitivity and intensity by using them together is also effective. Further, it is preferable to use a polymerizable compound having a trifunctional or higher functional group and different ethylene oxide chain lengths in that the developability of the photocurable composition can be adjusted and an excellent pattern forming ability can be obtained. . In addition, the selection of the polymerizable compound is also possible with respect to the compatibility and dispersibility with other components (for example, photopolymerization initiator, colorant (pigment), binder polymer, etc.) contained in the photocurable composition. The method of use is an important factor. For example, 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 from the viewpoint of improving adhesion to a hard surface such as a support.

<(B) Photopolymerization initiator>
The photocurable composition of the present invention contains a photopolymerization initiator such as a radical polymerization initiator.
The photopolymerization initiator imparts photosensitivity to the curable composition to form a photosensitive composition, and can be suitably used for a color resist or the like.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators, for example, visible from the ultraviolet region. Those having photosensitivity to light are preferable, and may be an activator that generates an active radical by causing some action with a photoexcited sensitizer, and initiates cationic polymerization according to the type of monomer. It may be an initiator.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within the range of about 300 to 800 nm (more preferably 330 to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime. Examples include oxime compounds such as derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole, etc.).

  In addition, as photopolymerization initiators other than those described above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbo Rubis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, etc.), acylphosphine oxides (for example, bis (2,4 , 6-Trimethylbenzoyl) -phenylphosphite Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl)- Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) Examples thereof include compounds described in JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. No. 3,615,455.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source of 365 nm or 405 nm can also be used. As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  More preferred examples of the photopolymerization initiator include oxime compounds. Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.

  Examples of oxime compounds such as oxime derivatives that are preferably used as a photopolymerization initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE-OXE-01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used as commercial products.

  Further, as oxime ester compounds other than those described above, compounds described in JP-T 2009-519904 in which oxime is linked to the carbazole N position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, and dyes A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced, a ketoxime compound described in International Publication No. 2009-131189, a triazine skeleton and an oxime skeleton are contained in the same molecule The compound described in US Pat. No. 7,556,910, the compound described in JP2009-221114A having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.

Preferably, it can also be suitably used for the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A. Among the cyclic oxime compounds, the cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A are particularly preferable in terms of high light absorption and high sensitivity.
In addition, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can achieve high sensitivity by regenerating an active radical from a polymerization inert radical, and can be suitably used. .

Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-267979 and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.
Specifically, the oxime photopolymerization initiator is preferably a compound represented by the following formula (1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

(In formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)
The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and , 3 Nitorofenashiru group can be exemplified.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, ter Nthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl , 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, 3H-indolyl, indolyl, 1H-indazolyl, purinyl 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxanthryl group.

  Specific examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.

  Specific examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, and a 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Two thiocarbonyl group, and a and a 4-methoxyphenylthiocarbonyl group.

  The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Of these, the structures shown below are particularly preferred.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (2) described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
Among these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the formula (1), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following formula (2).

(In formula (2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0-5. (It is an integer.)
R, A, and Ar in formula (2) have the same meanings as R, A, and Ar in formula (1), and preferred examples are also the same.

  Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among these, X is preferably an alkyl group from the viewpoints of solvent solubility and improvement in absorption efficiency in the long wavelength region.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

Examples of the divalent organic group represented by Y include the structures shown below. In the groups shown below, “” represents the bonding position between Y and an adjacent carbon atom in the formula (2).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

  Furthermore, the oxime compound is preferably a compound represented by the following formula (3).

(In formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5.)
R, X, A, Ar, and n in Formula (3) have the same meanings as R, X, A, Ar, and n in Formula (2), respectively, and preferred examples are also the same.

  Specific examples (C-4) to (C-13) of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.

  The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 455 nm.

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

You may use the photoinitiator used for this invention in combination of 2 or more type as needed.
The content of the photopolymerization initiator in the photocurable composition (the total content in the case of two or more) is in the range of 0.1 to 20% by mass with respect to the total solid content of the photocurable composition. Is preferable, more preferably in the range of 0.5 to 10% by mass, and particularly preferably in the range of 1 to 8% by mass. Within this range, good sensitivity and pattern formability can be obtained.

  The photocurable composition may contain a sensitizer for the purpose of improving the radical generation efficiency of the photopolymerization 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 photocurable composition include compounds described in paragraph numbers [0101] to [0154] of JP-A-2008-32803.
The content of the sensitizer in the photocurable composition is preferably 0.1% by mass to 20% by mass in terms of solid content from the viewpoints of light absorption efficiency to the deep part and initiation decomposition efficiency, and 0 More preferably, the content is 5% by mass to 15% by mass.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

<(C) Colorant>
The photocurable composition of the present invention may contain (C) a colorant. By containing a colorant, a colored photocurable composition having a desired color can be obtained.

  The colorant used in the photocurable composition of the present invention is not particularly limited, and various conventionally known dyes and pigments can be used singly or as a mixture of two or more, and these are photocurable. It is suitably selected according to the use of the composition. If the photocurable composition of the present invention is used in the production of a color filter, chromatic colorants (chromatic colorants) such as R, G, and B that form color pixels of the color filter, and a black matrix Any of the black colorants (black colorants) commonly used for formation can be used.

Hereinafter, the colorant that can be applied to the photocurable composition of the present invention will be described in detail using a colorant suitable for a color filter application as an example.
As the chromatic pigment, various conventionally known inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a finer one as much as possible, and considering the handling properties, the average primary particle diameter of the pigment is 0.01 μm. ˜0.1 μm is preferable, and 0.01 μm to 0.05 m is more preferable.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, Examples thereof include metal oxides such as silver and complex oxides of the above metals. Titanium nitrides, silver tin compounds, silver compounds, and the like can also be used.

Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.
C. I. Pigment YELLOW 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , Etc. 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279

C. I. Pigment Green 7, 10, 36, 37, 58
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80
C. I. Pigment Black 1
These organic pigments can be used alone or in various combinations in order to increase color purity.

In the photocurable composition of the present invention, when the colorant is a dye, a colored composition in a state of being uniformly dissolved in the composition can be obtained.
The dye that can be used as the colorant contained in the photocurable composition of the present invention is not particularly limited, and conventionally known dyes for color filters can be used. For example, pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, Dyes such as phthalocyanine, benzopyran, indigo, and pyromethene can be used. Moreover, you may use the multimer of these dyes.

Moreover, when performing water or alkali image development, an acidic dye and / or its derivative may be used suitably from a viewpoint that the binder and / or dye of a light non-irradiation part are removed completely by image development.
In addition, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, an oil-soluble dye, a food dye, and / or a derivative thereof can be usefully used.

Specific examples of the acid dye are shown below, but are not limited thereto. For example,
acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40-45, 62, 70, 74, 80, 83, 86 , 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chroma violet K; acid Fuchsin; acid green 1, 3, 5 , 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95;
red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91 , 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257 , 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; Food Yellow 3; and derivatives of these dyes.

  Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.

Among these, as the colorant, triarylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazole azo It is preferable that the colorant is selected from a series, anilinoazo, pyrazolotriazole azo, pyridone azo, and anthrapyridone pyromethene.
Further, pigments and dyes may be used in combination.

The colorant that can be used in the photocurable composition of the present invention is preferably a dye or a pigment. In particular, a pigment having an average particle size (r) of 20 nm ≦ r ≦ 300 nm, preferably 125 nm ≦ r ≦ 250 nm, particularly preferably 30 nm ≦ r ≦ 200 nm is desirable. By using a pigment having such an average particle diameter, a pixel having a high contrast ratio and a high light transmittance can be obtained. Here, the “average particle size” means the average particle size of secondary particles in which primary particles (single crystallites) of the pigment are aggregated. The average primary particle diameter can be obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.
The particle size distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter, simply referred to as “particle size distribution”) is 70% by mass of secondary particles having an average particle size of ± 100 nm. As mentioned above, it is desirable that it is 80 mass% or more. In the present invention, the particle size distribution was measured using the scattering intensity distribution.

  The pigment having the above average particle size and particle size distribution is preferably a commercially available pigment mixed with other pigments to be used (the average particle size usually exceeds 300 nm), preferably with a dispersant and a solvent. The pigment mixture can be prepared by mixing and dispersing while pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained is usually in the form of a pigment dispersion.

-Finer pigments-
In the present invention, a fine and sized organic pigment can be used as necessary. Finer pigments are prepared by preparing a high-viscosity liquid composition together with a pigment, a water-soluble organic solvent, and water-soluble inorganic salts, and applying a stress using a wet pulverizer and grinding. Achieved.

Water-soluble organic solvents used in the pigment refinement process include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Propylene glycol, propylene glycol monomethyl ether acetate and the like.
Further, as long as it is adsorbed to the pigment by being used in a small amount and is not washed away in the waste water, the water solubility is low or other solvents that are not water soluble, such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, Nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, halogenated hydrocarbons, acetone, methyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, or the like may be used.
Only one type of solvent may be used in the pigment refinement step, or two or more types may be mixed and used as necessary.

Examples of the water-soluble inorganic salt used in the pigment refinement step in the present invention include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.
The amount of the water-soluble inorganic salt used in the miniaturization step is 1 to 50 times by mass of the pigment, and a larger amount has a grinding effect, but a more preferable amount is 1 to 10 times by mass in terms of productivity. Moreover, it is preferable to use inorganic salts having a moisture content of 1% or less.
The usage-amount of the water-soluble organic solvent in a refinement | miniaturization process is the range of 50 mass parts to 300 mass parts with respect to 100 mass parts of pigments, Preferably it is the range of 100 mass parts to 200 mass parts.

  There are no particular restrictions on the operating conditions of the wet pulverizer in the pigment refinement process. However, in order to effectively carry out the grinding with the pulverizing media, the operating condition when the apparatus is a kneader is the rotational speed of the blade in the apparatus. Is preferably 10 to 200 rpm, and a relatively large biaxial rotation ratio is preferable because of its great grinding effect. The operation time is preferably 1 to 8 hours in combination with the dry grinding time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. Further, the water-soluble inorganic salt that is a pulverization medium preferably has a pulverization particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.

-Preparation of pigment-(Color matching)
These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment , A mixture with an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, or the like can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred. The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. In this range, the light transmittance from 400 nm to 500 nm can be suppressed, the color purity can be improved, and a sufficient coloring power can be achieved. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

  Further, as the green pigment, one kind of halogenated phthalocyanine pigment can be used alone or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. . For example, C.I. I. Pigment Green 7, 36, 37, 58 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200. In the above mass ratio range, the light transmittance of 400 to 450 nm can be suppressed, the color purity can be improved, the main wavelength does not become a long wavelength, and the hue in the vicinity of the NTSC target hue according to the home position. Can be obtained. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As the blue pigment, a single phthalocyanine pigment or a mixture of this and a dioxazine purple pigment can be used. As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

As the pigment, an inorganic pigment may be used. Examples of the inorganic pigment include a metal pigment, a metal-containing inorganic pigment made of a metal compound, a metal oxide, and the like, and carbon black.
Moreover, the photocurable composition of the present invention may be used not only for the formation of colored regions (pixels) of a color filter, but also for the formation of a black matrix. As a black pigment used in a composition for forming a black matrix, In addition to carbon, titanium black, iron oxide, titanium oxide, silver tin, silver, and the like, a pigment made of a metal mixture containing a metal oxide such as titanium oxide can be used.

The titanium black dispersion is described in detail below.
The titanium black dispersion is a dispersion containing titanium black as a coloring material.
By including titanium black in the photocurable composition as a titanium black dispersion prepared in advance, the dispersibility and dispersion stability of titanium black are improved.
Hereinafter, titanium black will be described.

-Titanium black-
Titanium black 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. .

  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, and still more preferably 20 to 200 nm from the viewpoint of dispersibility and colorability. .

The specific surface area of the titanium black is not particularly limited, but the water repellency after the surface treatment of the titanium black with a water repellent agent has a predetermined performance. Therefore, the value measured by the BET method is usually 5 to 150 m. ² / g approximately, and preferably from 20 to 100 m ² / g approximately.

  Examples of commercially available titanium black include, for example, Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, Ako Kasei Co., Ltd., Tilac D manufactured by Mitsubishi Materials Corporation. However, the present invention is not limited to these.

As content of the coloring agent contained in the photocurable composition of this invention, 20 mass%-95 mass% are preferable in the total solid of a photocurable composition, and 25 mass%-90 mass% are more. Preferably, 50 mass%-90 mass% is still more preferable, and 50 mass%-80 mass% is especially preferable.
By setting the content of the colorant in the above range, an appropriate chromaticity can be obtained when a color filter is produced from the photocurable composition. Further, since photocuring sufficiently proceeds and the strength as a film can be maintained, it is possible to prevent the development latitude during alkali development from becoming narrow.
That is, since the specific oxime compound (A) which is a polymerization initiator in the present invention has high light absorption efficiency, it is highly sensitive even when it contains a colorant in a high concentration in the photocurable composition. It can be polymerized and cured, and the effect of improving sensitivity is remarkably exhibited as compared with the case where other polymerization initiators are used.

<Pigment dispersant>
When the photocurable composition of the present invention contains a pigment as (C) a colorant, it is preferable to add (D) a pigment dispersant from the viewpoint of improving the dispersibility of the pigment.

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, naphthalene sulfonic acid formalin condensates], and surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, and pigment derivatives, etc. Can do.
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.

  Examples of the terminal-modified polymer having an anchor site to the pigment surface include polymers having a phosphate group at the terminal described in JP-A-3-112992, JP-T2003-533455, and the like. Examples thereof include a polymer having a sulfonic acid group at the terminal end described in JP-A-273191, and a polymer having a partial skeleton of an organic dye or a heterocyclic ring described in JP-A-9-77994. In addition, a polymer in which two or more anchor sites (acid group, basic group, partial skeleton of organic dye, heterocycle, etc.) to the surface of the pigment described in JP-A-2007-277514 are introduced. It is preferable because of excellent dispersion stability.

  Examples of the graft polymer having an anchor site to the pigment surface include poly (lower alkyleneimine) described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, and the like. ) And a polyester reaction product, a reaction product of polyallylamine and polyester described in JP-A-9-169821, etc., a macromonomer described in JP-A-10-339949, JP-A-2004-37986, and the like, Copolymers with nitrogen atom monomers, graft-type polymers having partial skeletons or heterocyclic rings of organic dyes described in JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, etc. And a copolymer of a macromonomer and an acid group-containing monomer described in JP2010-106268A. It is. In particular, the amphoteric dispersion resin having a basic group and an acidic group described in JP-A-2009-203462 exhibits dispersibility of the pigment dispersion, dispersion stability, and a photocurable composition using the pigment dispersion. Particularly preferred from the viewpoint of developability.

  As the macromonomer used when the graft polymer having an anchor site to the pigment surface is produced by radical polymerization, a known macromonomer can be used. Macromonomer AA-6 (terminal) manufactured by Toa Gosei Co., Ltd. Polymethyl methacrylate whose group is a methacryloyl group), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 ( Polybutyl acrylate whose end group is a methacryloyl group), PLACEL FM5 manufactured by Daicel Chemical Industries, Ltd. (5 molar equivalent addition product of ε-caprolactone of 2-hydroxyethyl methacrylate), FA10L (2-hydroxyethyl acrylate) ε-caprolactone 10 molar equivalent addition product), and JP-A-2-2720 Polyester macromonomer described in No. 09 publication. Among these, the polyester-based macromonomer that is particularly excellent in flexibility and solvent affinity is particularly preferable from the viewpoint of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the photocurable composition using the pigment dispersion. The polyester macromonomer represented by the polyester macromonomer described in JP-A-2-272009 is most preferable.

  As the block polymer having an anchor site to the pigment surface, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

  The pigment dispersant that can be used in the present invention is also available as a commercial product, and specific examples thereof include “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester)”, 110 (by BYK Chemie). Copolymer containing acid groups), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ) "EFKA 4047, 4050-4010-4165 (polyurethane)", EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid) Salt), 6220 (fatty acid polyester), 6745 Phthalocyanine derivatives), 6750 (azo pigment derivatives) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co.,“ Polyflow No. 50E, No. .300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA-703-50, manufactured by Enomoto Kasei Co., Ltd. DA-705, DA-725 "," Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "manufactured by Kao Corporation," Homogenol L- 18 (polymer polycarboxylic acid) "," Emulgen 920, 930, 935, 85 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine) ”manufactured by Nippon Lubrizol Co., Ltd. , 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate) ”manufactured by Nikko Chemicals, MYS-IEX (Polyoxyethylene monostearate), Kawaken Fine Chemical Co., Ltd. Hinoact T-8000E, Shin-Etsu Chemical Co., Ltd., Organosiloxane Polymer KP341, Yusho Co., Ltd. “W001: Cationic System Surfactant ", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester Nonionic surfactants such as glycerol propoxylate, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100 manufactured by Morishita Sangyo Co., Ltd.” EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 ", manufactured by San Nopco" Disperse Aid 6, Disperse Aid 8, Disperse " Polymeric dispersants such as Id 15 and Disperse Aid 9100, “ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101 manufactured by ADEKA Corporation , P103, F108, L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Chemical Co., Ltd., and the like.

  These pigment 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. The pigment dispersant of the present invention may be used in combination with an alkali-soluble resin together with a terminal-modified polymer, a graft polymer, or a block polymer having an anchor site to the pigment surface. Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples of the acid cellulose derivative include a resin having a hydroxyl group modified with an acid anhydride, and a (meth) acrylic acid copolymer is particularly preferable. Further, N-substituted maleimide monomer copolymers described in JP-A-10-300902, ether dimer copolymers described in JP-A-2004-300204, and polymerizable groups described in JP-A-7-319161. An alkali-soluble resin containing is also preferred.

As content of the pigment dispersant in a photocurable composition, it is preferable that it is 1-80 mass parts with respect to 100 mass parts of pigments which are colorants, 5-70 mass parts is more preferable, 10-60 More preferably, it is part by mass.
Specifically, if a polymer dispersant is used, the amount used is preferably in the range of 5 to 100 parts in terms of mass, and in the range of 10 to 80 parts, with respect to 100 parts by mass of the pigment. It is more preferable.
Moreover, when using together a pigment derivative, it is preferable that it is in the range of 1-30 parts in conversion of mass as a usage-amount of a pigment derivative, and is in the range of 3-20 parts with respect to 100 mass parts of pigments. A range of 5 to 15 parts is particularly preferable.

  In the photocurable composition, when a pigment as a colorant is used and a pigment dispersant is further used, from the viewpoint of curing sensitivity and color density, the total content of the colorant and the dispersant is the photocurable composition. It is preferably 30% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 90% by mass or less, and further preferably 50% by mass or more and 90% by mass or less with respect to the total solid content. preferable.

<Binder polymer>
In the photocurable composition of the present invention, a binder polymer can be further used as necessary for the purpose of improving the film properties.
It is preferable to use a linear organic polymer as the binder. 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.
An acrylic copolymer having an unsaturated group and an acid group is also preferable, and examples thereof include cyclomer P-ACA (manufactured by Daicel Chemical Industries, Ltd.), which is an acrylic copolymer resin having an acrylic group and a carboxyl group. it can.

  When an alkali-soluble resin is used as a copolymer, a monomer other than the above-mentioned monomers can also 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 acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as
(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.

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

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 binder polymers containing acid groups described in No. 271741 and Japanese Patent Application No. 10-116232, and urethane binder polymers having acid groups and double bonds in side chains as described in JP-A No. 2002-107918 Is excellent in strength, and is advantageous in terms of printing durability and suitability for low exposure.
In addition, the acetal-modified polyvinyl alcohol-based binder 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 binder polymer that can be used in the photocurable composition of the present invention is preferably 5,000 or more, more preferably in the range of 10,000 to 300,000, and the number average molecular weight is preferably It is 1,000 or more, More preferably, it is the range of 2,000-250,000. 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 binder polymer 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 the binder polymer that can be used in the photocurable composition of the present invention include known compounds such as an azo initiator and a peroxide initiator.

<Surfactant>
Various surfactants may be added to the photocurable composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, the photocurable composition of the present invention contains a fluorosurfactant, so that liquid properties (particularly fluidity) when prepared as a coating solution are further improved. And the liquid-saving property can be further improved.
That is, in the case of forming a film using a coating liquid to which a photocurable composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coating surface and the coating liquid, The wettability is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

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

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (above, manufactured by Asahi Glass Co., Ltd.).

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sol Perth 20000 (manufactured by Nippon Lubrizol Corporation), and the like.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.
Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the photocurable composition. .

<Polymerization inhibitor>
In the photocurable composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the curable composition.
Examples of the 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-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the whole composition.

<Adhesion improver>
In the photocurable composition of the present invention, 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.

  0.5-30 mass% is preferable in the total solid of a photocurable composition, and, as for the addition amount of a contact | adherence improving agent, 0.7-20 mass% is more preferable.

<Organic solvent>
In general, the photocurable composition of the present invention can be constituted using an organic solvent. The organic solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the photocurable composition, but in particular, considers the solubility, applicability, and safety of the UV absorber and binder. Are preferably selected. Moreover, when preparing the photocurable composition in this invention, it is preferable that at least 2 type of organic solvent is included.

  Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), 2- Xylpropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And as ethers For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone and aromatic hydrocarbons such as toluene, Xylene and the like are preferred.

  It is also preferable to mix two or more kinds of these organic solvents from the viewpoints of solubility of the ultraviolet absorber and the alkali-soluble resin, improvement of the coated surface, and the like. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  The content of the organic solvent in the photocurable composition is preferably such that the total solid concentration of the composition is 5 to 80% by mass, more preferably 5 to 60% by mass, from the viewpoint of applicability. 10 to 50% by mass is particularly preferable.

<Other additives>
Furthermore, in order to improve the physical properties of the cured film, known additives such as inorganic fillers, plasticizers, and oil sensitizers may be added to the photocurable 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.

  The photocurable composition of the present invention can be easily prepared by mixing and dissolving the above components in the above solvent by a known method.

As mentioned above, since the photocurable composition of this invention contains (A) specific polymeric compound, it hardens | cures with high sensitivity and the removability of an unexposed part at the time of alkali image development is also favorable.
For example, as in a color filter manufacturing method described later, a step of applying a photocurable composition to form a photocurable composition layer, a step of exposing the photocurable composition layer through a mask, and A pattern can be formed by the step of developing the photocurable composition layer after exposure.
Such a photocurable composition contains, in particular, (A) a specific polymerizable compound, (B) a photopolymerization initiator, and (C) a colorant to provide a photocurable composition for color filters (light for color filters). It is preferable to use it as a polymerizable composition).

<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 has a colored region (for example, a colored pattern) formed using the photocurable composition for a color filter on a support.
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).

  The method for producing a color filter of the present invention comprises a photocurable composition layer forming step of forming a photocurable composition layer by applying the photocurable composition of the present invention on a support, and the photocurable composition. An exposure step of exposing the physical layer in a pattern to cure the exposed portion, and a developing step of developing the curable composition layer after exposure to remove the uncured portion and forming a colored pattern. Including.

Specifically, the photocurable composition of the present invention (photocurable composition for color filters) is applied on a support (substrate) directly or via another layer, and then the photocurable composition layer. (Photocurable composition layer forming step), exposing through a predetermined mask pattern, curing only the light-irradiated coating film portion (exposure step), and developing with a developer (development step) ), A patterned film composed of pixels of each color (3 colors or 4 colors) can be formed to produce the color filter of the present invention.
Hereinafter, each process in the manufacturing method of the color filter of this invention is demonstrated.

[Photocurable composition layer forming step]
In the photocurable composition layer forming step, the photocurable composition of the present invention is applied on the support to form a photocurable 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 method for applying the photocurable composition for a color filter on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied. .

As a coating film thickness of the photocurable composition for color filters, 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 of the photocurable composition for color filters, 0.35 micrometers-1.5 micrometers are preferable from a viewpoint of resolution and developability, 0 More preferably, it is 40 μm to 1.0 μm.

  The photocurable composition for a color filter applied on a support is usually dried at 70 ° C. to 110 ° C. for about 2 minutes to 4 minutes to form a colored photocurable composition layer.

[Exposure process]
In the exposure step, the colored photocurable composition layer formed in the photocurable composition layer forming step is exposed in a pattern, and only the coating film portion irradiated with light is cured.
The exposure may be performed through a mask, as represented by UV exposure, or only a desired region may be exposed by using a laser or the like without using a mask.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is preferably 5 mJ to 1500 mJ, more preferably 10 mJ to 1000 mJ, and most preferably 10 mJ to 800 mJ.

[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, the uncured part is removed and 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.

  Examples of the alkali used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0. An alkaline aqueous solution obtained by diluting an organic alkaline compound such as] -7-undecene with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. 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 the method for producing a color filter of the present invention, after the above-described photocurable composition layer forming step, exposure step, and development step are performed, the formed colored pattern is heated and / or exposed as necessary. It may include a curing step for curing.

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

<Filter filtration>
The photocurable composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects.
As a filter used for filter filtration, if it is a filter conventionally used for the filtration use etc., it can use without being specifically limited.
Examples of the filter material include: a fluororesin such as PTFE (polytetrafluoroethylene); a polyamide resin such as nylon-6 and nylon-6, 6; a polyolefin resin such as polyethylene and polypropylene (PP) (high density, Including ultra high molecular weight); Among these materials, polypropylene (including high density polypropylene) is preferable.

The pore size of the filter is not particularly limited, but is, for example, about 0.01 to 20.0 μm, preferably about 0.01 to 5 μm, and more preferably about 0.01 to 2.0 μm.
By setting the pore size of the filter within the above range, fine particles can be more effectively removed and turbidity can be further reduced.
Here, the pore size of the filter can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .

In the filter filtration, two or more filters may be used in combination.
For example, the filtration can be performed first using a first filter and then using a second filter having a pore diameter different from that of the first filter.
At that time, the filtering by the first filter and the filtering by the second filter may be performed only once or may be performed twice or more, respectively.
As the second filter, a filter formed of the same material as the first filter described above can be used.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the color filter of the present invention.
Since the color filter of the present invention uses a photocurable composition for a color filter, the formed colored pattern exhibits high adhesion to a support substrate, and the cured composition is excellent in development resistance. It is possible to form a high-resolution pattern that is excellent in exposure 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.

The photocurable composition of the present invention can be suitably used for forming colored pixels such as color filters used in liquid crystal display devices (LCDs) and solid-state imaging devices (for example, CCDs, CMOSs, etc.). Moreover, it can use suitably also for image display devices, such as electronic paper and organic EL. In particular, it can be suitably used for forming color filters for solid-state imaging devices such as CCDs and CMOSs.
The photocurable composition of the present invention is particularly suitable for forming a color filter for a solid-state imaging device in which a colored pattern is formed in a thin film with a very small size and a good rectangular cross-sectional profile is required.

  The color filter of the present invention can be used in a liquid crystal display device or a solid-state imaging device, and is suitable for use in a liquid crystal display device. When the color filter of the present invention is used in a liquid crystal display device, color unevenness caused by the colorant occurs while containing a dye multimer containing a metal complex dye structure having excellent spectral characteristics and heat resistance as a colorant. It is suppressed, the color of the display image is good, and the display characteristics are excellent.

<Liquid crystal display device>
The color filter of the present invention is suitable as a color filter for a liquid crystal display device. A liquid crystal display device provided with such a color filter can display a high-quality image having a good display image color tone and excellent display characteristics.

  For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention is useful for a color TFT type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
The color filter of the present invention can also be used for a bright and fine COA (Color-filter On Array) system. The colored layer formed by the COA method has a rectangular shape with a side length of about 1 to 15 μm in order to connect the ITO electrode arranged on the colored layer and the terminal of the driving substrate below the colored layer. It is necessary to form a conduction path such as a through hole or a U-shaped depression, and the dimension of the conduction path (that is, the length of one side) is particularly preferably 5 μm or less, but by using the present invention, It is also possible to form a conduction path of 5 μm or less. These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

The liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display element composed of these known members. Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding the backlight, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Have been described.

  When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, but further, red, green and blue LED light sources (RGB-LED). By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

  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” and “%” are based on mass.

  First, specific polymerizable compounds A to G and comparative compounds 1 to 3 which are polymerizable compounds used in Examples and Comparative Examples are shown below.

  The specific polymerizable compounds A to G were synthesized by the following method.

(Synthesis Example: Synthesis of Compound A)
Ethylene glycol (14.9 g, 0.24 mol) and N-hydroxymethylacrylamide (50 g, 0.5 mol) are dissolved in 100 ml of toluene, and then oxalic acid (0.5 g, 4 mmol) is added, and the mixture is heated at 100 ° C. for 5 hours. Heated. Subsequently, the reaction solution was cooled to room temperature, 100 ml of saturated sodium bicarbonate water was added, and the mixture was stirred for 30 minutes. After removing the aqueous layer by a liquid separation operation, the organic phase was washed with water, dried and concentrated to obtain a crude product. This was purified by column chromatography to obtain 58 g of Compound (A).

As for the specific compound (B) to the specific compound (G), in the synthesis method of the specific compound (A), ethylene glycol is replaced with a polyfunctional alcohol compound described in the list of raw materials for the polymerizable compound, and N-hydroxymethylacrylamide is used. Was synthesized in the same manner except that the input amount of was changed to the number of alcohol functional groups of the polyfunctional alcohol compound × 1.02 × 0.24 mol.

[Examples 1-1 to 1-15, Comparative Examples 1-1 to 1-3]
[1. Preparation of photocurable composition]
As a photocurable composition for forming a color filter, a negative photocurable composition containing a colorant (pigment) was prepared, and a color filter was produced using the negative photocurable composition.

1-1. Preparation of pigment dispersion (P1)-composition P1-
Pigment C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 219 30/70 (mass ratio) mixture 40 parts by mass Dispersant
BYK2001 10 parts by mass (Disperbyk: manufactured by Big Chemie (BYK),
Solid content concentration: 45.1% by mass; approximately 4.51 parts by mass in terms of solid content)
・ Solvent 150 parts by mass of ethyl 3-ethoxypropionate

  A mixed liquid composed of the composition P1 was mixed and dispersed for 15 hours by a bead mill to prepare a pigment dispersion (P1).

  With respect to the obtained pigment dispersion (P1), the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 200 nm.

1-2. Preparation of photocurable composition (coating solution)

<Composition A-1>
The following components were mixed and dissolved to prepare a photocurable composition A-1.
-(C) Colorant [Pigment dispersion (P1)] 700 parts by mass-(G) Binder polymer 100 parts by mass [Benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10, weight Average molecular weight: 10,000]
-(A) Polymerizable compound 60 parts by mass [As shown in Table 1, the specific polymerizable compound A and comparative compound 1 (dipentaerythritol hexaacrylate; trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 1: 1 (mass ratio) was used, and the total amount was 60 parts by mass. ]
-(B) Oxime-based photopolymerization initiator (trade name: IRGACURE OX-01, BASF) 60 parts by mass-Solvent (propylene glycol monomethyl ether acetate) 1000 parts by mass-Surfactant [trade name: Tetranic 150R1, BASF Company] 1 part by mass / γ-methacryloxypropyltriethoxysilane 5 parts by mass

<Compositions A-2 to A-15 and a-1 to a-3>
Compositions A-2 to A-15 and a-1 to a-3 were prepared in the same manner as the composition A-1, except that the polymerizable compound shown in Table 1 was used. When two kinds of polymerizable compounds are used in combination, the total amount is 60 parts by mass with a mass ratio of 1: 1, and in the case of a single compound, the amount is 60 parts by mass with a single polymerizable compound.

[2. (Production of color filter)
2-1. Formation of Photocurable Composition Layer Each of the colored photocurable compositions containing the pigment obtained as described above was applied as a resist solution to a 550 mm × 650 mm glass substrate by slit coating under the following conditions, and then left as it was for 10 minutes. And then subjected to vacuum drying and prebaking (100 ° C., 80 seconds) to form a photocurable composition coating film (photocurable composition layer).

(Slit application conditions)
Gap at the opening at the tip of the coating head: 50 μm
Coating speed: 100 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry thickness): 2 μm
Application temperature: 23 ° C

2-2. Exposure, Development The curable layer formed as described above is subjected to line width of 1.2 μm / line width of 1.7 μm / line width of 2.0 μm / line using an i-line exposure apparatus FPA-3000i5 (manufactured by Canon Inc.). Exposure using a photomask for Bayer pattern test with a width of 2.2 μm, and after exposure, the entire surface of the curable layer is a 60% aqueous solution of an organic developer (trade name: CD2000, manufactured by Fuji Film Electronics Materials Co., Ltd.). And then rested for 60 seconds.

2-3. Heat treatment Subsequently, pure water was sprayed onto the photocurable composition layer in a shower to wash away the developer, and then heated in an oven at 220 ° C. for 1 hour (post-bake). Thereby, a color filter having a colored pattern on the glass substrate was obtained.

3. Performance Evaluation The curability, substrate adhesion, developability, and wrinkles of the resulting colored pattern when a colored pattern was formed on a glass substrate using the photocurable composition were evaluated as follows. The evaluation results are summarized in Table 1.

3-1. Curability The minimum exposure amount in which the film thickness after development of the region irradiated with light in the exposure step was 95% or more with respect to 100% of the film thickness before exposure was evaluated as exposure sensitivity. The smaller the value of exposure sensitivity, the better the curability and the better the sensitivity.

<Evaluation criteria>
A: The exposure sensitivity was less than 300 mJ / cm ² .
△: exposure sensitivity was ^{300mJ / cm 2 ~1000mJ / cm 2} .
X: The exposure sensitivity was over 1000 mJ / cm ² .

3-2. Development by confirming the substrate surface and the cross-sectional shape after post-baking in developability, substrate adhesion, and pattern wrinkle "2-3. Heat treatment" with an optical microscope and SEM photograph observation in a usual manner. Property, substrate adhesion, and pattern wrinkle were evaluated. Details of the evaluation method are as follows.

<Board adhesion>
In a Bayer pattern with a line width of 1.2 μm / line width of 1.7 μm / line width of 2.0 μm / line width of 2.2 μm, whether or not a pattern defect has occurred is observed with a microscope, and according to the following evaluation criteria: The substrate adhesion after post-baking was evaluated.
This evaluation of substrate adhesion is based on the case of using a curable composition before storage (initial), and the case of using a curable composition after storage for 1 month at room temperature and further storage at 45 ° C. for 3 days. And both.
Table 1 shows the results for the Bayer pattern having a line width of 1.7 μm or less (that is, a line width of 1.2 μm and a line width of 1.7 μm).
-Evaluation criteria-
○: No pattern defect was observed.
Δ: Slight pattern defects were confirmed, but there was no problem in practical use. X: Pattern defects were remarkably observed.

<Developability>
In the exposure step, the developability was evaluated by observing the presence or absence of development residues in the areas not irradiated with light (unexposed areas). The results are shown in Table 1 below.
-Evaluation criteria-
○: Residue was not confirmed at all in the unexposed area. Δ: Residue was slightly confirmed at the unexposed area, but there was no practical problem. confirmed

<Wrinkle pattern>
The condition of the surface of the formed pattern was observed and evaluated.
-Evaluation criteria-
○: Wrinkles were not confirmed on the surface of the pattern. Δ: Wrinkles were confirmed on the surface of the pattern, but there was no problem in practical use. ×: Wrinkles were remarkably confirmed on the surface of the pattern.

  From the result of Table 1, the photocurable composition of each Example containing specific polymerizable compounds A to G has high adhesion, and developability (development residue) when using a colored pattern of a color filter for formation. It can be seen that it is excellent both in suppression of occurrence), curability and pattern wrinkles.

[Examples 2-1 to 2-15, Comparative examples 2-1 to 2-3]
[1. Preparation of resist solution
Components of the following composition were mixed and dissolved to prepare a resist solution.
-Composition of resist solution-
・ Propylene glycol monomethyl ether acetate (PGMEA)
19.20 parts by mass / ethyl lactate 36.67 parts by mass / resin 30.51 parts by mass [benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22/18) 40 % PGMEA solution]
Dipentaerythritol hexaacrylate (polymerizable compound) (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 12.20 parts by mass Polymerization inhibitor (p-methoxyphenol) 0.0061 parts by mass Fluorine-based surface activity 0.83 parts by mass of agent (F-475, manufactured by DIC Corporation)
-Photopolymerization initiator 0.586 parts by mass (TAZ-107 (trihalomethyltriazine photopolymerization initiator), manufactured by Midori Chemical Co., Ltd.)

[2. Fabrication of silicon wafer substrate with undercoat layer]
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.

[3. Preparation of photocurable composition (coating liquid)]
<Composition B-1>
The following components were mixed and dissolved to prepare a photocurable composition B-1 containing a colorant (dye).
-80 parts by mass of cyclohexanone-Colorant C.I. I. Acid Blue 108 7.5 parts by mass / colorant C.I. I. Solvent Yellow 162 2.5 parts by mass / specific polymerizable compound: Compound A 3.5 parts by mass / polymerizable compound: Comparative Compound 1 3.5 parts by mass / oxime photopolymerization initiator: IRGACURE OXE-2.5 2.5 parts by mass Parts / glycerol propoxylate (surfactant) 0.5 parts by mass (number average molecular weight Mn: 1500, molar extinction coefficient ε = 0)

<Compositions B-2 to B-15 and b-1 to b-3>
Compositions B-2 to B-15 and b-1 to b-3 were prepared in the same manner as the composition B-1, except that the polymerizable compound shown in Table 2 was used. When two kinds of polymerizable compounds are used in combination, the total amount is 7.0 parts by mass with a mass ratio of 1: 1, and in the case of a single compound, 7.0 parts by mass with a single polymerizable compound.

[4. (Production and evaluation of color filter)
3 above. For each of the photocurable compositions prepared in 1. above, It was applied on the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in (1) to form a photocurable coating film. Then, a heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.9 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), irradiation was performed at an exposure dose of 10 to 1600 mJ / cm ² through an Island pattern mask having a pattern of 2 μm square at a wavelength of 365 nm.
Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (FUJIFILM Corporation). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

A silicon wafer substrate on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotational speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the rotation center in the form of a shower through a spray nozzle, followed by rinsing treatment, and then spray drying.
As described above, a color filter having a colored pattern formed on the substrate was obtained.

  About the obtained photocurable composition and color filter, evaluation similar to Example 1-1 was performed. The results are shown in Table 2.

  From the result of Table 2, the photocurable composition of each Example containing specific polymeric compound AG has high adhesiveness, and developability (color of a development residue) when using the coloring pattern of a color filter for formation. It can be seen that it is excellent both in suppression of occurrence), curability and pattern wrinkles.

[Examples 3-1 to 3-15, Comparative example 3-1 to Comparative example 3-3]
<Composition C-1>
The following compounds were mixed and dissolved to prepare a photocurable composition C-1 containing a colorant (pigment).
-Solvent ethyl 3-ethoxypropionate 17.9 mass parts-(C) Coloring agent C.I. I. Pigment Red 254 Pigment Dispersion 26.7 parts by mass (solid content: 15%, pigment content in solid content: 60%)
C. I. Pigment Yellow 139 Pigment Dispersion 17.8 parts by mass (solid content: 15%, pigment content in solid content: 60%)
-(A) Polymerizable compound 1: 1 mixture of specific polymerizable compound A and comparative compound 1 (mass ratio) 3.5 parts by mass-(B) oxime-based photopolymerization initiator IRGACURE OX-01 0.5 parts by mass -(G) Binder polymer benzyl methacrylate / methacrylic acid copolymer 2.0 parts by mass [molar ratio = 70/30, weight average molecular weight: 30000]

<Compositions C-2 to C-15 and c-1 to c-3>
Compositions C-2 to C-15 and c-1 to c-3 were prepared in the same manner as the composition C-1, except that the polymerizable compound shown in Table 3 was used. When two kinds of polymerizable compounds are used in combination, the total amount is 3.5 parts by mass with a mass ratio of 1: 1, and in the case of a single compound, the amount is 3.5 parts by mass with a single polymerizable compound.

<Production and evaluation of color filter>
Using the photocurable composition thus prepared, a color filter was produced in the same manner as in Example 2-1, and the same evaluation as in Example 1-1 was performed. The results are shown in Table 3 below.

  From the result of Table 3, the photocurable composition of each Example containing specific polymerizable compounds A to G has high adhesiveness, and developability (development residue) when a colored pattern of a color filter is used for formation. It can be seen that it is excellent both in suppression of occurrence), curability and pattern wrinkles.

[Example 4-1 to Example 4-15, Comparative Example 4-1 to Comparative Example 4-4]
<Composition D-1> (High pigment concentration)
The following compounds were mixed and dissolved to prepare a photocurable composition D-1 containing a colorant (pigment).
-Solvent ethyl 3-ethoxypropionate 17.9 mass parts-(C) Coloring agent C.I. I. Pigment Red 254 pigment dispersion (solid content: 15%, pigment content in solid content: 60%) 33.34 parts by mass C.I. I. Pigment Yellow 139 pigment dispersion (solid content: 15%, pigment content in solid content: 60%) 22.23 parts by mass (A) polymerizable compound 1: 1 of specific polymerizable compound A and comparative compound 1 Mixture (mass ratio) 2.5 parts by mass (B) Oxime-based photopolymerization initiator
IRGACURE OX-01 0.5 parts by mass. (G) Binder polymer 2.0 parts by mass of benzyl methacrylate / methacrylic acid copolymer [molar ratio = 70/30, weight average molecular weight: 30000]

<Preparation of compositions D-2 to D-15 and d-1 to d-3> (High pigment concentration)
Compositions D-2 to D-15 and d-1 to d-3 were prepared in the same manner as the composition D-1, except that the polymerizable compound shown in Table 4 was used. When two types of polymerizable compounds are used in combination, the total amount is 2.5 parts by mass with a mass ratio of 1: 1, and when it is a single compound, it is 2.5 parts by mass with a single polymerizable compound.

<Production and evaluation of color filter>
Using the prepared photocurable composition, a color filter was produced in the same manner as in Example 2-1, and the same evaluation as in Example 1-1 was performed. The results are shown in Table 4 below.

  From the result of Table 4, the photocurable composition of each Example containing specific polymeric compound AG has high adhesiveness, and developability (color of a development residue) when using the coloring pattern of a color filter for formation. It can be seen that it is excellent both in suppression of occurrence), curability and pattern wrinkles.

[Example 5]
<Composition E-1>
The following compounds were mixed and dissolved to prepare a photocurable composition E-1.
Propylene glycol monomethyl ether acetate 69.82 parts by mass Cyclomer P-ACA (unsaturated group and acid group-containing acrylic copolymer resin, solid content 50% by mass, weight average molecular weight 30000, manufactured by Daicel Chemical Industries, Ltd.)
13.66 parts by mass- (A) polymerizable compound 1: 1 mixture of specific polymerizable compound E and comparative compound 1 (mass ratio) 10.25 parts by mass- (B) oxime-based photopolymerization initiator [trade name: CGI-124, BASF Corporation]
0.98 parts by mass-The following compound (ultraviolet absorber) 1.03 parts by mass-Surfactant (Fluorine-based surfactant; manufactured by DIC Corporation, product name Megafax F-144)
0.01 part by mass / polymerization inhibitor (p-methoxyphenol; manufactured by Kanto Chemical Co., Ltd., product name p-methoxyphenol) 0.0051 part by mass

<Compositions E-2 and e-1 to e-3>
Compositions E-2 and e-1 to e-3 were prepared in the same manner as the composition E-1, except that the polymerizable compounds shown in Table 3 were used. When two types of polymerizable compounds are used in combination, the total amount is 10.25 parts by mass with a mass ratio of 1: 1, and in the case of a single compound, the amount is 10.25 parts by mass with a single polymerizable compound.
The obtained photocurable composition was evaluated in the same manner as in Example 1-1, and the results are shown in Table 5 below.

  From the results of Table 5, the photocurable composition of each Example containing a specific polymerizable compound has high adhesion even when it does not contain a colorant, and developability (development residue) when a pattern is used for formation. It can be seen that it is excellent both in curbing of the occurrence of selenium), curability and pattern wrinkles.

[Example 6]
<Production of full-color color filter>
-Formation of black matrix-
In the preparation of the photocurable composition B-1 of Example 2-1, the black light for the black matrix was similarly obtained except that the total 10.0 parts by mass of the colorant was replaced by 10 parts by mass of carbon black. A curable composition K-1 was prepared.
Further, in the formation of the colored pattern of Example 2-1, the black matrix was similarly obtained except that the photocurable composition B-1 was replaced with the black photocurable composition K-1 prepared as described above. Formed.

On the black matrix obtained as described above, a 2 μm square green (G) coloring pattern was formed in the same manner as in the method described in Example 2-1, using the photocurable composition B-1. Formed.
Furthermore, in the photocurable composition A-1, only a pigment (30/70 [mass ratio] mixture of CI Pigment Green 36 and CI Pigment Yellow 219) is used as a blue pigment (C.I. I. Pigment Blue 15: 6 and CI Pigment Violet 23 30/70 [mass ratio] mixture) and red pigment (CI Pigment Red 254) Blue (B) and red (R) photocurable compositions were prepared.
First, a 2 μm square blue (B) and red (R) pattern is sequentially formed on the substrate in the same manner as in the case of the green (G) photocurable composition B-1, and the color for the solid-state imaging device. A filter was produced.

  About the obtained full-color color filter, when the development residue of each of the black matrix pattern and the colored pattern of each color of RGB was evaluated in the same manner as in Example 1-1, no development residue was found. It was also found that the substrate adhesion was excellent.

[Example 7]
<Production of solid-state image sensor>
When the full-color color filter obtained in Example 6 was incorporated into a solid-state imaging device, it was confirmed that the solid-state imaging device had high resolution and excellent color separation.

Claims (11)

(A) A photocurable composition containing a radical polymerizable compound represented by the following general formula (1) and (B) a photopolymerization initiator.
[In General Formula (1), a plurality of R ₁ independently represent a hydrogen atom or a methyl group, and a plurality of R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or an organic group, X in the formula independently represents an oxygen atom or a sulfur atom, Y represents an n-valent organic linking group, and n represents an integer of 2 or more and 11 or less. ]   The photocurable composition according to claim 1, wherein n in the general formula (1) is an integer of 3 or more and 7 or less.   (C) The photocurable composition of Claim 1 or 2 which further contains a coloring agent.   (C) The photocurable composition according to claim 3, wherein the colorant is a chromatic colorant.   (C) A coloring agent is a black coloring agent, The photocurable composition of Claim 3.   (B) The photocurable composition of any one of Claims 1-5 containing an oxime type photoinitiator as a photoinitiator.   (C) Content of a coloring agent is 50 to 90 mass% with respect to the total solid of a photocurable composition, The photocurable composition of any one of Claims 3-6 object.   The process of apply | coating the photocurable composition of any one of Claims 1-7, and forming a photocurable composition layer, The process of exposing the said photocurable composition layer through a mask, The pattern formation method characterized by including the process of developing the said photocurable composition layer after exposure.   The color filter which has a coloring pattern formed using the photocurable composition of any one of Claims 3-7 on a support body.   The process of apply | coating the photocurable composition of any one of Claims 3-7 on a support body, and forming a photocurable composition layer, and the said photocurable composition layer through a mask And a step of developing the photocurable composition layer after the exposure to form a colored pattern.   A solid-state imaging device comprising the color filter according to claim 9.