JP2016145977A - Colored photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition having good solubility with a developer in an unexposed part, from which a sharp pattern profile can be produced and a high-definition color filter having high brightness in a thin film state can be provided.SOLUTION: The colored photosensitive resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and contains, as the colorant (A), C.I. Pigment Green 58, C.I. Pigment Yellow 185 and C.I. Pigment Yellow 138.SELECTED DRAWING: None

Description

  The present invention relates to a green colored photosensitive resin composition. In particular, as a colorant (A), C.I. I. Pigment green 58, C.I. I. Pigment yellow 185 and C.I. I. The present invention relates to a colored photosensitive resin composition containing CI Pigment Yellow 138.

  In recent years, display displays have been developed to widen the color gamut that can be displayed, and as part of this, color filters having a darker color are required. In order to satisfy the requirement, there is a method of increasing the color material concentration in the color filter. However, when the color material concentration increases, the performance as a colored photosensitive resin composition deteriorates, such as the deterioration of the pattern shape. It is not preferable. In addition, in order to have the desired color characteristics, it is necessary to produce a color filter with a thick film. However, when applied to a liquid crystal display device, a color mixture of light with adjacent pixels occurs. Membrane formation is also not preferable.

  In Patent Document 1, C.I. I. Pigment Green 58 and C.I. I. Pigment blue 15: 3 and C.I. I. A green photosensitive resin composition containing a colorant containing CI Pigment Yellow 150, a resin, a polymerizable monomer, a photopolymerization initiator and a solvent is described.

JP 2012-247539 A

  The present invention provides a colored photosensitive resin composition having good solubility in a developer in an unexposed portion, capable of producing a clear pattern shape, and capable of providing a high-definition color filter having high brightness while being a thin film. The issue is to provide.

  As a result of intensive studies, the present inventors have found that a colored photosensitive resin composition capable of solving the above problems can be obtained, and have completed the present invention.

That is, this application discloses the following invention.
[1] Including a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
As the colorant (A), C.I. I. Pigment green 58, C.I. I. Pigment yellow 185 and C.I. I. A colored photosensitive resin composition comprising Pigment Yellow 138.
[2] C.I. I. Pigment Yellow 185 is the colored photosensitive resin composition according to [1], in which particles having a particle size of 100 nm or more have a particle size distribution of 5% by mass or less.
[3] The colored photosensitive resin composition according to [1] or [2], wherein the total amount of the colorant (A) is 20 to 50% by mass in 100% by mass of the solid content of the colored photosensitive resin composition. .
[4] The colored photosensitive resin composition according to any one of [1] to [3], further including a thiol compound (T).
[5] The polymerization initiator (D) is at least two selected from an O-acyloxime compound, an alkylphenone compound, a biimidazole compound, a triazine compound, and an acylphosphine oxide compound. The colored photosensitive resin composition in any one.
[6] The resin (B) is a copolymer including a structural unit derived from the monomer (b) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond. [5] The colored photosensitive resin composition according to any one of [5].
[7] A coating film formed from the colored photosensitive resin composition according to any one of [1] to [6].
[8] A color filter formed from the colored photosensitive resin composition according to any one of [1] to [6].
[9] A display device including the color filter according to [8].

  According to the present invention, a colored photosensitive resin composition having good solubility in an unexposed portion of a developer, capable of producing a clear pattern shape, and capable of providing a high-definition color filter having high brightness while being a thin film You can get things.

The colored photosensitive resin composition according to the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) is a green pigment. C. I. Pigment Green 58 and C.I. I. Pigment yellow 185 and C.I. I. Pigment Yellow 138 is included.
The colored photosensitive resin composition according to the present invention preferably further contains a solvent (E).
The colored photosensitive resin composition according to the present invention preferably further contains a thiol compound (T).
Moreover, it is preferable that the colored photosensitive resin composition which concerns on this invention contains a leveling agent (F) further.
In addition, unless otherwise indicated, the compound illustrated as each component in this specification can be used individually or in combination of multiple types.

<Colorant (A)>
The colored photosensitive resin composition according to the present invention includes C.I. I. Pigment Green 58, C.I. I. Pigment yellow 185 and C.I. I. Pigment yellow 138.

In the colored photosensitive resin composition, C.I. I. It is preferable that the pigment yellow 185 has a particle size distribution in which particles having a particle size of 100 nm or more are 5% by mass or less. When the content of particles having a particle diameter of 100 nm or more is within the above range, a good coating film having a low retardation value can be obtained. Particles having a particle size of 100 nm or more are more preferably 4% by mass or less, further preferably 3.5% by mass or less, particularly preferably 3% by mass or less, and most preferably 2.5% by mass or less. is there.
The particle size of the pigment can be reduced by adding mechanical strength to the pigment.
For example, mechanical strength can be added to a pigment by stirring the pigment in an organic solvent. When the pigment is stirred using a bead mill, the particle size can be easily adjusted. The stirring time necessary for preparing the pigment exhibiting the particle size distribution can be determined by measuring the particle size distribution described later. The preferred stirring time varies depending on the amount and type of the pigment, but generally the particle size can be made smaller by increasing the stirring time. In addition, it is possible to efficiently add mechanical strength to the pigment by increasing the stirring speed.

Note that C.I. I. The particle size and particle size distribution of Pigment Yellow 185 can be determined by, for example, the following method.
1) Propylene glycol monomethyl ether acetate, acrylic pigment dispersant and C.I. I. Pigment Yellow 185 and thoroughly agitating with a bead mill, the C.I. I. Pigment Yellow 185 is dispersed. C. in mixed dispersion. I. The concentration of Pigment Yellow 185 is 5% by mass, and the concentration of the acrylic pigment dispersant is 3.5% by mass.
2) The obtained mixed dispersion was diluted 50 times with propylene glycol monomethyl ether acetate, then measured at 25 ° C. with a dynamic light scattering measurement device (Zetasizer Nano ZS; manufactured by Malvern), and the pigment was determined from the scattering intensity. The particle size and the particle size distribution of are calculated. Polystyrene latex is used as the standard substance.

C. I. Pigment Green 58 and C.I. I. The content ratio of CI Pigment Yellow 185 (CI Pigment Yellow 185 / CI Pigment Green 58) is preferably 1% or more, more preferably 3% or more, and still more preferably 5% or more in terms of mass ratio. % Or less is preferable, 25% or less is more preferable, and 20% or less is still more preferable.
C. I. Pigment Green 58 and C.I. I. The content ratio of CI Pigment Yellow 138 (CI Pigment Yellow 138 / CI Pigment Green 58) is preferably 1% or more, more preferably 1.5% or more, and still more preferably 2% or more by mass ratio. 70% or less is preferable, 65% or less is more preferable, and 60% or less is still more preferable.

C. I. The content of pigment green 58 is usually preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and 98% by mass or less in the total 100% by mass of the colorant (A). Preferably, 90 mass% or less is more preferable, and 85 mass% or less is still more preferable.
C. I. The content of Pigment Yellow 185 is usually preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and further preferably 20% by mass or less in the total 100% by mass of the colorant (A). Preferably, 18 mass% or less is more preferable, and 16 mass% or less is still more preferable.
C. I. The content of Pigment Yellow 138 is usually preferably 0.3% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, in the total 100% by mass of the colorant (A). % By mass or less is preferred, 38% by mass or less is more preferred, and 35% by mass or less is still more preferred.
In addition, the sum total of a coloring agent (A) makes an upper limit 100 mass%.

C. I. The content of Pigment Green 58 is usually preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 24% by mass or more, and 45% by mass in 100% by mass of the solid content in the composition. The following is preferable, More preferably, it is 40 mass% or less, More preferably, it is 35 mass% or less.
C. I. The content of Pigment Yellow 185 is usually 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more, in 100% by mass of the solid content in the composition. It is preferably at most mass%, more preferably at most 20 mass%, still more preferably at most 10 mass%.
C. I. The content of Pigment Yellow 138 is usually 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more, in a solid content of 100% by mass in the composition. 30 mass% or less is preferable, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.

C. I. Pigment yellow 185 and C.I. I. When the total amount of CI Pigment Yellow 138 is 100% by mass, C.I. I. Pigment Yellow 185 is preferably 10% by mass or more and 90% by mass or less. C. I. When the content of Pigment Yellow 185 is within this range, the development type is good.
In the present specification, the “total amount of solids” refers to the total amount of components obtained by removing the solvent (E) from the colored photosensitive resin composition of the present invention. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

  C. I. Pigment green 58, C.I. I. Pigment yellow 185 and C.I. I. Any of Pigment Yellow 138, if necessary, rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment to the pigment surface with a polymer compound, etc., sulfuric acid atomization method Or the like, or a cleaning process using an organic solvent or water for removing impurities, a removal process using an ion exchange method for ionic impurities, or the like may be performed.

  In the present invention, the pigment is preferably used in the form of a pigment dispersion in which the pigment is uniformly dispersed in a solvent. The pigment dispersion can be obtained by mixing the pigment in a solvent. If necessary, a pigment dispersant may be mixed in the pigment dispersion. In mixing, C.I. I. Pigment green 58, C.I. I. Pigment yellow 185 and C.I. I. Pigment Yellow 138 may be mixed singly or in combination.

The pigment dispersant may be any of cationic, anionic, nonionic, and amphoteric dispersants, and examples thereof include polyester-based, polyamine-based, and acrylic-based pigment dispersants.
These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by BASF), Ajispur (Ajinomoto Fine) (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.
When the pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion in which the pigment is uniformly dispersed in the solvent tends to be obtained.

It does not specifically limit as said solvent, The solvent similar to the solvent (E) in the colored photosensitive resin composition of this invention is mentioned (it mentions later for details). Among them, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and the like are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3 Ethyl ethoxypropionate are more preferable.
Although the usage-amount of a solvent is not specifically limited, It is good to use a solvent so that solid content concentration in a pigment dispersion liquid can be adjusted to 3-20 mass%, More preferably, it can be adjusted to 5-18 mass%.

  The method for preparing the pigment dispersion is not particularly limited, and (i) C.I. I. Pigment green 58, C.I. I. Pigment yellow 185 and C.I. I. By mixing each of CI Pigment Yellow 138 in a solvent. I. Pigment Green 58 pigment dispersion, C.I. I. Pigment Yellow 185 pigment dispersion, C.I. I. Pigment Yellow 138 pigment dispersion may be used, and (ii) C.I. I. Pigment green 58, C.I. I. Pigment yellow 185 and C.I. I. C. by mixing all of Pigment Yellow 138 in a solvent. I. Pigment green 58, C.I. I. Pigment yellow 185 and C.I. I. A pigment dispersion containing three types of CI Pigment Yellow 138 may be used.

  Examples of the colorant (A) include C.I. I. Pigment green 58, C.I. I. Pigment yellow 185 and C.I. I. Besides Pigment Yellow 138, known pigments and dyes can also be used. In the present invention, C.I. I. Pigment green 58, C.I. I. Pigment yellow 185 and C.I. I. The total use amount of Pigment Yellow 138 is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, in 100% by mass of the colorant (A). Preferably it is 80 mass% or more, More preferably, it is 90 mass% or more, Most preferably, it is 100 mass%.

  The total amount of the colorant (A) is preferably 20 to 50% by mass, more preferably 25 to 47% by mass, and further preferably 35 to 45% by mass in 100% by mass of the solid content of the colored photosensitive resin composition. %.

<Resin (B)>
Although it does not specifically limit as resin (B), It is preferable that it is alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1] At least one (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and a cyclic ether structure having 2 to 4 carbon atoms And a monomer (b) (hereinafter sometimes referred to as “(b)”) having an ethylenically unsaturated bond.
Resin [K2] (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) In some cases).
Resin [K3] Copolymer of (a) and (c).
Resin [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c).
Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c).
Resin [K6] A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include acrylic acid containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.

(B) has, for example, a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. It refers to a polymerizable compound. (B) is preferably a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.

  (B1) is, for example, a monomer (b1-1) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon (hereinafter sometimes referred to as “(b1-1)”), an unsaturated alicyclic hydrocarbon And a monomer (b1-2) (hereinafter sometimes referred to as “(b1-2)”) having an epoxidized structure.

  As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by Formula (I), and Formula (II) The compound etc. which are represented by these are mentioned.

[In Formula (I) and Formula (II), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group May be substituted.
X ¹ and X ² each independently represent a single bond, * —R ^c —, * —R ^c —O—, * —R ^c —S—, * —R ^c —NH—.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— (* represents a bond to O), or * —CH ₂ CH ₂ —O— group. More preferably, a single bond and a * —CH ₂ CH ₂ —O— group are mentioned.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I-11) to Formula (I-15) Is mentioned. More preferably, Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9), Formula (II-11) to Formula (II-15) Is mentioned. More preferably, Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) are mentioned.

  The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. They can also be mixed in any ratio. When mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 in the formula (I): formula (II). ~ 80: 20.

  As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

  As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2. 2.1] hept-2-ene and the like are preferable. Moreover, since it is excellent in the developability at the time of pattern formation, benzyl (meth) acrylate and tricyclodecyl (meth) acrylate are more preferable.

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].
Structural unit derived from (a); 2 to 50 mol% (more preferably 10 to 45 mol%)
Structural unit derived from (b); 50 to 98 mol% (more preferably 55 to 90 mol%)
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability, developability, and solvent resistance of the resulting pattern tend to be excellent.

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and stirred, heated, and kept warm in a deoxygenated atmosphere. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) As the solvent, any solvent capable of dissolving each monomer may be used, and a solvent (E) described later can be used as a solvent for the colored photosensitive resin composition.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using a solvent (E) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

In the resin [K2], the ratio of the structural units derived from each is preferably within the following range among all the structural units constituting the resin [K2].
Structural unit derived from (a); 4-45 mol% (more preferably 10-30 mol%)
Structural unit derived from (b); 2-95 mol% (more preferably 5-80 mol%)
Structural unit derived from (c); 1 to 65 mol% (more preferably 5 to 60 mol%)
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability, developability, solvent resistance of the resulting pattern, heat resistance, and mechanical strength tend to be excellent.

Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].
Specifically, a predetermined amount of (a), (b) and (c), a polymerization initiator, and a solvent are charged into a reaction vessel, and the mixture is stirred, heated and kept warm in a deoxygenated atmosphere. As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. May be used.

In the resin [K3], the ratio of the structural unit derived from each is preferably in the following range among all the structural units constituting the resin [K3].
(A) 2 to 55 mol%, more preferably 10 to 50 mol%
(C) 45-98 mol%, more preferably 50-90 mol%
Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (a) has a carboxylic acid and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms that (b) has It can manufacture by adding to.
First, a copolymer of (a) and (c) is produced in the same manner as described in the method for producing resin [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).
(A) 5 to 50 mol%, more preferably 10 to 45 mol%
(C) 50 to 95 mol%, more preferably 55 to 90 mol%

Next, the C2-C4 cyclic ether which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( (Dimethylaminomethyl) phenol and the like) and a polymerization inhibitor (for example, hydroquinone and the like) are placed in a flask and reacted at, for example, 60 to 130 ° C. for 1 to 10 hours to obtain a resin [K4]. .
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity to become favorable. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 mass% with respect to the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5% by mass with respect to the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

Resin [K5] obtains a copolymer of (b) and (c) as a first step in the same manner as in the method for producing resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c) is preferably in the following range with respect to the total number of moles of all structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol% (more preferably 10-90 mol%)
Structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%)

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid anhydride of (a). Resin [K5] can be obtained by reacting the product.
As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5]. Carboxylic anhydride is reacted with a hydroxy group generated by reaction of cyclic ether with carboxylic acid or carboxylic anhydride.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (highmic acid anhydride) and the like. It is done.

As the resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- ( Resin [K2] such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / (meth) a Resin [K3] such as crylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer; benzyl (meth) Resin with glycidyl (meth) acrylate added to acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate added to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin, resin such as resin obtained by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer [K4]; tricyclodecyl (meth) acrylate / (Meth) acrylic acid is reacted with a copolymer of glycidyl (meth) acrylate Resin, such as resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate [K5]; tricyclodecyl (meth) acrylate / glycidyl (meth ) A resin [K6] such as a resin obtained by further reacting a copolymer of acrylate with (meth) acrylic acid and a tetrahydrophthalic anhydride, and the resin [K1] is preferred.
These resins may be used alone or in combination of two or more.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is in the above range, the solubility of the unexposed part in the developer tends to be high, and the remaining film ratio and hardness of the resulting pattern tend to be high.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The solution acid value of the resin (B) is preferably 5 to 180 mg-KOH / g, more preferably 10 to 100 mg-KOH / g, and still more preferably 12 to 50 mg-KOH / g. Here, the acid value of the solution is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined by, for example, titration using an aqueous potassium hydroxide solution.

  The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% in the solid content of 100% by mass of the colored photosensitive resin composition. % By mass. When content of resin (B) exists in the said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to be high.

<Polymerizable compound (C)>
The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by an active radical or the like generated from the polymerization initiator (D) by being irradiated with light, for example, polymerizable ethylenically unsaturated Examples thereof include a compound having a bond. The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less, for example.

  Among these, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meta ) Acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol Tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate And caprolactone-modified dipentaerythritol hexa (meth) acrylate. Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like can be given.

  The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass, more preferably 25 to 120 parts by mass with respect to 100 parts by mass of the resin (B) in the colored photosensitive resin composition. .

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include an O-acyl oxime compound, an alkylphenone compound, a biimidazole compound, a triazine compound, and an acyl phosphine oxide compound.

  The O-acyloxime compound is a compound having a structure represented by the formula (d1). Hereinafter, * represents a bond.

  Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among these, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. When these O-acyloxime compounds are used, a color filter with high brightness tends to be obtained.

  The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having the structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) ) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, and the like. It is done. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.
Examples of the compound having a structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy ) Phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone, benzyl Examples thereof include dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d2).

  Examples of the biimidazole compound include compounds represented by the formula (d5).

[In formula (d5), R ^{13 to} R ¹⁸ represent an aryl group having 6 to 10 carbon atoms which may have a substituent. ]

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferable.
Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, Preferably it is a chlorine atom. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, Preferably it is a methoxy group.
Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4,4. ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4' , 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2- Chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) Biimidazole (for example , Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), an imidazole compound in which the phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group (for example, JP, 7-10913, A) etc. are mentioned. Among these, compounds represented by the following formula and mixtures thereof are preferable.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl). ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2- Methylphenyl) Sulfonyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

The colored photosensitive resin composition of the present invention preferably contains at least two or more selected from the group consisting of an O-acyloxime compound, an alkylphenone compound and a biimidazole compound as the polymerization initiator (D), and more preferably. Includes O-acyloxime compounds and biimidazole compounds.
When the polymerization initiator (D) includes an O-acyl oxime compound and a biimidazole compound, the total content of the O-acyl oxime compound and the biimidazole compound is preferably relative to the total amount of the polymerization initiator (D). Is 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, particularly preferably 80% by mass or more, and most preferably 100% by mass.

  When using at least 2 or more types selected from the compound group which consists of a polymerization initiator (D) and a thiol compound (T), a 1st main component (compound with the highest content ratio) and a 2nd main component (1st main) The content ratio of the component and the compound having the same content ratio or the second highest content ratio) is preferably from 1: 9 to 9: 1, more preferably from 2: 8 to 8: 2, and even more preferably, on a mass basis. Is 4: 6 to 6: 4.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass of the total amount of the resin (B) (solid content) and the polymerizable compound (C). Is 1-20 parts by mass, more preferably 2-15 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the color filter is improved.

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-di. Examples include butoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

As the polymerization initiation assistant (D1), a thioxanthone compound is preferable.
When using these polymerization initiation assistants (D1), the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Preferably it is 1-20 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

<Thiol compound (T)>
The thiol compound (T) is a compound having a sulfanyl group (—SH) in the molecule.

  Examples of the compound having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, 2 -Sulfanylpyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4- Amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4 Diamino-6-sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanylpyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl- 6-propylpyrimidine, 2-sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2 -Sulfanylimidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino-5-sulfanyl-1,2,4-triazole, 2 -Methyl-4H-1,2,4- Riazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-sulfanyl-1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl- 1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl) methanethiol, 2 -Sulfanyl-5-thiazolidone, 2-sulfanylthiazoline, 2-sulfanyl-4 (3H) -quinazolinone, 1-phenyl-1H-tetrazol-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2-sulfanyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5 Chloro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2-sulfanylbenzothiazole, 2-sulfanylnaphthimidazole, 2-sulfanylnaphthoxazole, 3-sulfanyl-1,2,4- Triazole, 4-amino-6-sulfanylpyrazolo [2,4-d] pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo [2,4-d] pyrimidine, etc. Is mentioned.

  Compounds having two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl) Acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), tri Methylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), tris Mud carboxyethyl tris (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3-sulfanyl-butyloxy) include butane and the like.

  The content of the thiol compound (T) is preferably 0.5 to 50 parts by mass, more preferably 5 to 45 parts by mass, and still more preferably 10 to 40 parts per 100 parts by mass of the polymerization initiator (D). Part by mass. When the content of the thiol compound (T) is within this range, sensitivity tends to be high and developability tends to be good.

<Solvent (E)>
The colored photosensitive resin composition of the present invention preferably contains a solvent (E). A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, ester solvents (solvents containing —COO—), ether solvents other than ester solvents (solvents containing —O—), ether ester solvents (solvents containing —COO— and —O—), ketones other than ester solvents A solvent (solvent containing —CO—), an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, or the like can be selected and used.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate and the like.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. Etc.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

These solvents may be used alone or in combination of two or more.
Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and the like are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3 Ethyl ethoxypropionate are more preferable.

  The content of the solvent (E) in the colored photosensitive resin composition is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass. In other words, the solid content of the colored photosensitive resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good.

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants and fluorine surfactants. These may have a polymerizable group in the side chain.

  Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) .

  Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone surfactant further include a silicone surfactant having a fluorine atom. Specific examples of the silicone surfactant having a fluorine atom include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

  The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass in the total amount of the colored photosensitive resin composition. Hereinafter, it is more preferably 0.01% by mass or more and 0.05% by mass or less. This content does not include the content of the pigment dispersant.

<Antioxidant (J)>
From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to use an antioxidant alone or in combination of two or more. The antioxidant is not particularly limited as long as it is an antioxidant generally used industrially, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used.
Examples of the phenol-based antioxidant include Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation), Irganox. 1076 (Irganox 1076: octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Corporation), Irganox 1330 (Irganox 1330: 3, 3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, manufactured by BASF Corp.), Irganox 3114 (Irganox 3114: 1,3,5-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, manufactured by BASF), Irganox 3790 (Irganox 3790: 1,3,5-Tris) ((4-tert-butyl-3-hydroxy-2,6-xylyl) methyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, manufactured by BASF Corp.) Irganox 1035 (Irganox 1035: thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation), Irganox 1135 (Irganox 1135: benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, BASF ), Irganox 1520L (Irganox 1520L: 4,6-bis (octylthiomethyl) -o-cresol, manufactured by BASF), Irganox 3125 (Irganox 3125, manufactured by BASF), Irganox 565 (Irganox 565: 2,4-bis (n-octylthio) -6- (4-hydroxy 3 ′, 5′-di-tert-butylanilino) -1,3,5-triazine, manufactured by BASF Corporation), ADK STAB AO-80 (ADK STAB AO-80: 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2 , 4,8,10-tetraoxaspiro (5,5) undecane, manufactured by ADEKA Corporation), Sumilizer BHT (Sumilizer BHT, manufactured by Sumitomo Chemical Co., Ltd.), Sumilyzer GA-80 (Sumizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), Sumilyzer GS (Sumizer GS, manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox 1790, (Product of Cytec Co., Ltd.) and vitamin E (manufactured by Eisai Co., Ltd.).
Examples of the phosphorus antioxidant include Irgafos 168 (Irgafos 168: Tris (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Corporation), Irgafos 12 (Irgafos 12: Tris [2-[[ 2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine (manufactured by BASF Corporation), Irgaphos 38 (Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by BASF Corp.), ADK STAB 329K (manufactured by ADEKA Corp.), ADK STAB PEP36 (Manufactured by ADEKA), ADK STAB PEP-8 (manufactured by ADEKA), Sandstab PE PQ (manufactured by Clariant), Weston 618 (Weston 618, manufactured by GE), Weston 619G (manufactured by Weston 619G, manufactured by GE), Ultranox 626 (manufactured by Ultranox 626, manufactured by GE), and Sumilizer GP (Sumilizer GP: 6- [ 3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1.3.2] dioxaphosphine Pin) (manufactured by Sumitomo Chemical Co., Ltd.).
Examples of the sulfur-based antioxidant include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and β-alkyl mercaptopropionic acids of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane. An ester compound etc. are mentioned.

<Other ingredients>
In the colored photosensitive resin composition of the present invention, if necessary, a filler, a polymer compound other than the resin (B), an adhesion promoter, an ultraviolet absorber, an aggregation inhibitor, an organic acid, an organic amine compound, curing An additive such as an agent can also be used in combination.

  Specific examples of the filler include glass, silica, and alumina.

  Examples of the polymer compound other than the resin (B) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

  Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

  Examples of the ultraviolet absorber include benzotriazole compounds such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole; 2-hydroxy-4-octyloxybenzophenone Benzophenone compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2- (4,6-diphenyl-1,3, And triazine compounds such as 5-triazin-2-yl) -5-hexyloxyphenol;

  Specific examples of the aggregation inhibitor include sodium polyacrylate.

The organic acid is used for adjusting developability, specifically,
Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid , Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid;
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
And aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid.

Examples of the organic amine compound include:
n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine Monoalkylamines such as n-undecylamine and n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, di- dialkylamines such as n-pentylamine and di-n-hexylamine;
Monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;
Dicycloalkylamines such as dicyclohexylamine;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n -Trialkylamines such as butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine;
Dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;
Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine;
Monoalkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol ;
Monocycloalkanolamines such as 4-amino-1-cyclohexanol;
Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine;
Dicycloalkanolamines such as di (4-cyclohexanol) amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine;
Tricycloalkanolamines such as tri (4-cyclohexanol) amine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 Aminoalkane diols such as 2, 2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol;
Amino group-containing cycloalkanone methanol such as 1-aminocyclopentanone methanol, 4-aminocyclopentanone methanol;
Amino group-containing cycloalkanemethanol such as 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid;
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, pn-butylaniline, p-tert-butylaniline, 1- Aromatic amines such as naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, aminobenzoic acid such as p-diethylaminobenzoic acid; and the like.

  Examples of the curing agent include a compound that can react with the carboxy group in the resin (B) by being heated to crosslink the resin (B), a compound that can be polymerized alone to cure the colored pattern, and the like. Can be mentioned. Examples of the compound include an epoxy compound and an oxetane compound.

Here, as the epoxy compound, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, other aromatic type epoxy resin, fat Aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oils, brominated derivatives of these epoxy resins, fats other than epoxy resins and their brominated derivatives Aliphatic, alicyclic or aromatic epoxy compounds, epoxidized butadiene (co) polymers, epoxidized isoprene (co) polymers, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanurate Etc.
Examples of commercially available epoxy resins include orthocresol novolac type epoxy resins, “Sumiepoxy (registered trademark) ESCN-195XL-80” (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

  Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  When the colored photosensitive resin composition of the present invention contains an epoxy compound, an oxetane compound, or the like as a curing agent, it may contain a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. Good. Examples of the compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators.

As the polyvalent carboxylic acid,
Phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3 ', 4,4'-benzophenone tetra Aromatic polycarboxylic acids such as carboxylic acids;
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid Alicyclic polycarboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid; and the like.

As the polyvalent carboxylic acid anhydride,
Aromatic polycarboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride;
Aliphatic polycarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride ;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polycarboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride and nadic anhydride;
And ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitic acid and glycerol tristrimellitic anhydride.

As said carboxylic acid anhydride, you may use what is marketed as an epoxy resin hardening | curing agent. As said epoxy resin hardening | curing agent, brand name "Adeka Hardener (registered trademark) EH-700" (made by ADEKA), brand name "Rikacid (registered trademark) HH" (made by Shin Nippon Rika Co., Ltd.), Product name “MH-700” (manufactured by Shin Nippon Rika Co., Ltd.) and the like.
Examples of acid generators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl benzylsulfonium. Onium salts such as hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate Examples include rates.

  The above curing agents may be used alone or in combination of two or more.

<Method for producing colored photosensitive resin composition>
The colored photosensitive resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E) used as necessary, and a thiol compound. It can be prepared by mixing (T), a leveling agent (F), a polymerization initiation assistant (D1), an antioxidant (J), and other components.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored photosensitive resin composition of the present invention include a photolithographic method, an ink jet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the colored photosensitive resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.

  As a substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate Further, aluminum, silver, a silver / copper / palladium alloy thin film or the like is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored photosensitive resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. Further, the heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.
The film thickness of the colored composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.
A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.
Furthermore, it is preferable to post-bake the obtained colored pattern. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

  Since the film thickness of the obtained coating film affects adjacent pixels, the coating film is preferably as thin as possible. In particular, when the film is thick, the light from the light source may leak through the pixels of two or more colors when the liquid crystal panel is manufactured. May be lost. The coating film after post-baking is preferably 3.5 μm or less, more preferably 3.2 μm or less. Although the minimum of a coating film is not specifically limited, Usually, 1 micrometer or more may be 1.5 micrometers or more.

  Moreover, the lightness of a coating film is so high that it is preferable, 45 or more are preferable, More preferably, it is 47 or more, and although an upper limit is not specifically limited, Usually, it is 70 or less, and 58 or less may be sufficient.

Moreover, it is preferable that a coating film shows a high value in the contrast evaluation shown below, Specifically, Usually, it is 1000 or more, 5000 or more are preferable, More preferably, it is 5500 or more, Although an upper limit is not specifically limited. Usually, it is 35000 or less.
[Contrast evaluation]
About the coating film, using a contrast meter (CT-1: Osaka Co., Ltd., color difference meter BM-5A: manufactured by Topcon Corporation, light source: F-10, polarizing film: Osaka Co., Ltd.) When the measurement is performed without using a film, the measurement is performed so as to be 50000.

Further, the coating film preferably shows a low value in the retardation evaluation shown below, specifically, usually 70 nm or less, preferably 50 nm or less, more preferably 40 nm or less, and the lower limit is usually 1 nm or more. It may be 3 nm or more.
[Phase difference evaluation]
The coating film is measured using a phase difference measuring device (ellipsometer; manufactured by JASCO Corporation) under the conditions of a measurement wavelength of 550 nm and a refractive index of 1.5. Rth, which is a phase difference, is calculated from the following equation.
Rth = {(Nx + Ny) / 2−Nz} × d

  The colored coating film and colored pattern formed by the colored photosensitive resin composition of the present invention are useful as a color filter. The color filter is used as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention. In the following, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

Synthesis example 1
An appropriate amount of nitrogen was passed through a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 280 parts by mass of propylene glycol monomethyl ether acetate was added and heated to 80 ° C. with stirring. Next, 38 parts by mass of acrylic acid, 289 parts by mass of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 and / or 9-yl acrylate, 125 parts of propylene glycol monomethyl ether acetate Part of the mixed solution was added dropwise over 5 hours. On the other hand, a mixed solution in which 33 parts by mass of 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in 235 parts by mass of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the completion of dropping, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature. Got. The produced copolymer had a weight average molecular weight Mw of 9,200 and a dispersity of 2.08.

About the measurement of polystyrene conversion weight average molecular weight Mw of resin obtained by said synthesis example, it carried out on condition of the following using GPC method.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation)

[Preparation of pigment dispersion (A-1)]
C. I. Pigment Green 58 13.0 parts Acrylic pigment dispersant 2.0 parts Propylene glycol monomethyl ether acetate 85.0 parts were mixed, and the particle size distribution of the pigment was measured. As a result, particles having a particle size of 100 nm or more were 22 in total. The pigment dispersion liquid (A-1) was obtained by stirring the pigment using a bead mill until the ratio reached%.

[Preparation of pigment dispersion (A-2)]
C. I. Pigment Yellow 185 5.0 parts Acrylic pigment dispersant 3.5 parts Propylene glycol monomethyl ether acetate 91.5 parts were mixed and the particle size distribution of the pigment was measured. The pigment dispersion liquid (A-2) was obtained by stirring the pigment using a bead mill until the ratio reached%.

[Preparation of pigment dispersion (A-3)]
C. I. Pigment Yellow 185 5.0 parts Acrylic pigment dispersant 3.5 parts Propylene glycol monomethyl ether acetate 91.5 parts were mixed and the particle size distribution of the pigment was measured. The pigment dispersion liquid (A-3) was obtained by stirring the pigment using a bead mill until the ratio reached%. The stirring time for preparing the pigment dispersion (A-3) was shorter than that of the pigment dispersion (A-2).

[Preparation of pigment dispersion (A-4)]
C. I. Pigment Yellow 138 15.0 parts Acrylic pigment dispersant 4.5 parts Propylene glycol monomethyl ether acetate 80.5 parts were mixed and the particle size distribution of the pigment was measured. The pigment dispersion liquid (A-4) was obtained by stirring the pigment using a bead mill until the ratio reached%.

[Preparation of pigment dispersion (A-5)]
C. I. Pigment Yellow 150 11.9 parts Acrylic pigment dispersant 5.4 parts Propylene glycol monomethyl ether acetate 82.7 parts were mixed and the particle size distribution of the pigment was measured. The pigment dispersion liquid (A-5) was obtained by stirring the pigment using a bead mill until the ratio reached%.

[Preparation of pigment dispersion (A-6)]
C. I. Pigment Green 7 11.0 parts Acrylic pigment dispersant 3.3 parts Propylene glycol monomethyl ether acetate 85.7 parts were mixed, and the particle size distribution of the pigment was measured. The pigment dispersion liquid (A-6) was obtained by stirring the pigment using a bead mill until the ratio reached%.

  In the preparation of the pigment dispersion described above, the particle size and particle size distribution of the pigment were measured by the following procedure: After the obtained pigment dispersion was diluted 50 times with propylene glycol monomethyl ether acetate, dynamic light was used. It measured at 25 degreeC with the scattering measuring apparatus (Zetasizer nano ZS; product made from Malvern), and calculated the particle size and particle size distribution of the pigment from scattering intensity. Polystyrene latex was used as a standard material.

[Preparation of colored photosensitive resin composition]
Examples 1-4 and Comparative Examples 1-3
The components shown in Table 1 were mixed to obtain a colored photosensitive resin composition. In addition, propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored photosensitive resin composition was “solid content (%)” in Table 1.

In Table 1, each component is as follows.
Colored dispersion (A1); Pigment dispersion (A-1) obtained above
Colored dispersion (A2); Pigment dispersion (A-2) obtained above
Colored dispersion (A3); Pigment dispersion (A-3) obtained above
Colored dispersion (A4); Pigment dispersion (A-4) obtained above
Colored dispersion (A5); Pigment dispersion (A-5) obtained above
Colored dispersion (A6); Pigment dispersion (A-6) obtained above
Resin solution (B1); copolymer obtained in Synthesis Example 1 polymerizable compound (C1); dipentaerythritol hexaacrylate (KAYARAADDPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D1); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE01; manufactured by BASF; O-acyloxime compound)

  Polymerization initiator (D2); mixture of compounds represented by the following formula (CHEMCURE-TCDM; manufactured by Cambridge; biimidazole compound)

  Thiol compound (T1); 2-sulfanylbenzothiazole (Soxinol M; manufactured by Sumitomo Chemical Co., Ltd .; compound represented by the following formula)

  Leveling agent (F1); polyether-modified silicone oil (SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Preparation of coating film]
Using the colored photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3, coating films were prepared according to the following procedure.
Preparation procedure: A colored photosensitive resin composition was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning), and then prebaked at 100 ° C for 3 minutes. After cooling, the substrate coated with the colored photosensitive resin composition is irradiated with light using an exposure machine (TME-150RSK; manufactured by Topcon Corporation) at an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. did. After light irradiation, the resulting film was developed by immersing it in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 24 ° C. for 60 seconds, washed with water, In the inside, it post-baked at 230 degreeC for 30 minutes, and obtained the green coating film.

[Film thickness measurement]
About the coating film obtained from the colored photosensitive resin composition of Examples 1-4 and Comparative Examples 1-3, film thickness FT (micrometer) using a film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). Was measured. The results are shown in Table 2.

[Chromaticity evaluation]
About each coating film obtained from the coloring photosensitive resin composition of Examples 1-4 and Comparative Examples 1-3, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Corporation make). The xy chromaticity coordinates (x, y) and the brightness Y in the CIE XYZ color system were measured using the characteristic function of the F10 light source.
It is x = 0.29 and y = 0.66 in the chromaticity coordinates by repeating coating film preparation and chromaticity evaluation and adjusting the spin coat rotation speed when applying the colored photosensitive resin composition. A coating film was obtained. The results of the color characteristics of the obtained coating film are shown in Table 2.

[Contrast evaluation]
About each coating film obtained from the colored photosensitive resin composition of Examples 1 to 3 and Comparative Example 1, contrast meter (CT-1: Keyakizaka Electric Co., Ltd., color difference meter BM-5A: manufactured by Topcon Corporation, Contrast was measured using a light source: F-10, a polarizing film: Osaka Electric Co., Ltd.). The blank value at the time of measurement is 50000. The results are shown in Table 3.

[Phase difference evaluation]
About the coating film obtained from the colored photosensitive resin composition of Examples 1-3 and the comparative example 1, a measurement wavelength is 550 nm and refractive index is 1. using a phase difference measuring apparatus (ellipsometer; JASCO Corporation make). The measurement was performed under the condition of 5. The results are shown in Table 3.

[Preparation of pattern]
Using each colored photosensitive resin composition of Examples 1 to 4 and Comparative Examples 1 to 3, patterns were prepared according to the following procedure.
Production procedure: A colored photosensitive resin composition was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) so as to have the film thickness shown in Table 2, and then dried under reduced pressure. The machine was dried under reduced pressure up to 130 Pa. Thereafter, the distance between the substrate coated with the colored photosensitive resin composition and the quartz glass photomask having the pattern is set to 100 μm, and using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), in an air atmosphere, Light irradiation was performed at an exposure amount of 150 mJ / cm ² (based on 365 nm). As a photomask, a mask on which a 50 μm line and space pattern was formed was used. After light irradiation, the coating film was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, and 230 ° C. in an oven. And post-baking for 30 minutes to produce a pattern.

[Development type]
During the pattern preparation, the solubility of the unexposed portion in the developer was confirmed when immersed in the developer. Evaluation was made as “◯” when dissolved in the developer, and “X” when solids peeled off from the glass substrate with the peeled pieces were confirmed. The results are shown in Table 2.

[Pattern production availability]
When a 30 μm pattern is obtained in the line and space pattern produced by the same method as described in [Preparation of pattern] above, “◯”, the exposed part is peeled off or dissolved, and a 30 μm pattern is formed. When it did not remain, it evaluated as "x". The results are shown in Table 2.

  From the colored photosensitive resin compositions of Examples 1 to 4, it was confirmed that the film thickness was in an appropriate range and a coating film excellent in lightness could be formed. Moreover, when forming a pattern, the peeling piece did not generate | occur | produce but the solubility to a developing solution was favorable, and it was also confirmed that developability is favorable. Furthermore, it was confirmed that the colored photosensitive resin compositions of Examples 1 to 3 can form a coating film having a low phase difference and a high contrast.

  On the other hand, regarding the coating films obtained from the colored photosensitive resin compositions of Comparative Examples 1 to 3, it was confirmed that when the pattern was formed, peeling pieces were generated in the unexposed areas and the solubility in the developer was not good. It was. The coating film obtained from the colored photosensitive resin composition of Comparative Example 1 could not obtain a practical retardation or contrast. Since the film thickness obtained from each colored photosensitive resin composition of Comparative Examples 2 and 3 has a film thickness exceeding 3.5 μm, the utility is low. In addition, when a pattern was produced from these colored photosensitive resin compositions, the pattern could not be formed because peeling and dissolution of the exposed portion occurred.

  According to the colored photosensitive resin composition of the present invention, it is possible to produce a pattern having good solubility and good shape in a developing solution in an unexposed portion, and further, a high-definition having high brightness while being a thin film. A color filter can be manufactured.

Claims (9)

A colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D);
As the colorant (A), C.I. I. Pigment green 58, C.I. I. Pigment yellow 185 and C.I. I. A colored photosensitive resin composition comprising Pigment Yellow 138.   C. I. The colored photosensitive resin composition according to claim 1, wherein Pigment Yellow 185 has a particle size distribution in which particles having a particle size of 100 nm or more are 5% by mass or less.   The colored photosensitive resin composition according to claim 1 or 2, wherein the total amount of the colorant (A) is 20 to 50% by mass in 100% by mass of the solid content of the colored photosensitive resin composition.   Furthermore, the colored photosensitive resin composition of any one of Claims 1-3 containing a thiol compound (T).   The said polymerization initiator (D) is 2 or more types chosen from an O-acyl oxime compound, an alkylphenone compound, a biimidazole compound, a triazine compound, and an acyl phosphine oxide compound. The colored photosensitive resin composition as described.   The resin (B) is a copolymer containing a structural unit derived from the monomer (b) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond. The colored photosensitive resin composition according to item 1.   The coating film formed from the colored photosensitive resin composition of any one of Claims 1-6.   The color filter formed from the colored photosensitive resin composition of any one of Claims 1-6.   A display device comprising the color filter according to claim 8.