JP6950478B2 - Photosensitive coloring compositions and color filters for color filters - Google Patents

Description

A liquid crystal display panel having a high transmittance structure has been developed, which employs a color filter-on array (COA) substrate in which a color filter is formed on an array substrate. The COA method can significantly increase the aperture ratio and achieve high image quality and low power consumption of the color liquid crystal display device. However, since it is necessary to provide a contact hole in the pixel for connecting the transparent electrode and the TFT in the COA type pixel, the photosensitive coloring composition for a color filter forming the pixel needs to have better resolution.
A method of using a specific initiator for improving the resolution (see Patent Document 1), a composition for a color filter using a benzotriazole-based ultraviolet absorber (see Patent Document 2), and the like are disclosed. However, in recent years, the importance of high color reproducibility has increased as a required quality item, and it has become necessary to increase the content of the colorant in the resist. However, when the content of the colorant increases, the irradiation light at the time of exposure However, the boundary (edge of the formed pattern) of the photosensitive coloring composition for a color filter is not sufficiently cured, and pattern chipping in which some of the pixels are missing is likely to occur. Therefore, if the amount of the photopolymerization initiator is increased to cure the photosensitive coloring composition for a color filter to the pixel boundary, the contact hole is closed and the transparent electrode and the TFT cannot be connected, so that a COA type color liquid crystal display device cannot be manufactured. .. Furthermore, since the resolution of the contact hole is lowered due to the increase in the non-developable colorant, it is necessary to increase the amount of the photopolymerizable monomer. Since the adhesion with the light is lowered, pattern peeling is likely to occur. Therefore, the COA method has a problem of producing a high-resolution pattern without causing pattern peeling or pattern chipping as compared with a normal color filter.

Japanese Unexamined Patent Publication No. 2001-324611 Japanese Unexamined Patent Publication No. 2000-214580

In particular, the present invention uses a photosensitive coloring composition for a color filter having excellent adhesion that does not cause pattern peeling or pattern chipping, and a photosensitive coloring composition thereof, which is required to have excellent high resolution such as the COA method. The purpose is to provide a color filter that has been used.

As a result of intensive research to solve the above problems, the present inventors have conducted diligent research.
Photosensitivity for color filters containing colorant (A), resin (B) (excluding resin (I)), photopolymerizable monomer (C), photopolymerization initiator (D) and solvent (E) It is a coloring composition
Further, at least one selected from the group consisting of the antioxidant (F) and the polymerization inhibitor (G), and
The content of the colorant (A) containing at least one selected from the group consisting of the phosphoric acid ester compound (H) having an ethylenically unsaturated group and the amino group-containing resin (I) is photosensitive for a color filter. It is 25% by mass to 45% by mass with respect to the total solid content of the coloring composition.
A photosensitive coloring composition for a color filter having a content of the photopolymerizable monomer (C) of 30% by mass to 55% by mass with respect to the total solid content of the photosensitive coloring composition for a color filter.
The photopolymerizable monomer and the colorant can suppress the thickening of the pixel even with a large amount of the photosensitive colorant, and the photopolymerizable initiator is applied to the entire photosensitive colorant without blocking the contact holes of the pixels, which is important in the COA method. Since it is possible to increase the amount, curing proceeds to the boundary of the pixels, and by adding a phosphoric acid ester compound having an ethylenically unsaturated group and an amino group-containing resin, the adhesion to the substrate is improved and the photopolymerization unit is used. Since the amount of the monomer can be increased, it has been found that a photosensitive coloring composition for a color filter having excellent high resolution and excellent adhesion that does not cause pattern peeling or pattern chipping and a color filter using the same are provided. The present invention has been made based on the findings.

<1> A color filter containing a colorant (A), a resin (B) (excluding the resin (I)), a photopolymerizable monomer (C), a photopolymerization initiator (D), and a solvent (E). Photosensitive coloring composition for use
Further, it is composed of at least one selected from the group consisting of an antioxidant (F) and a polymerization inhibitor (G), a phosphoric acid ester compound (H) having an ethylenically unsaturated group, and an amino group-containing resin (I). The content of the colorant (A) containing at least one selected from the group is 25% by mass or more and 45% by mass or less with respect to the total solid content of the photosensitive coloring composition for a color filter, and is photopolymerizable. A photosensitive coloring composition for a color filter in which the content of the monomer (C) is 30% by mass or more and 55% by mass or less with respect to the total solid content of the photosensitive coloring composition for a color filter.

<2> The total content of the antioxidant (F) and the polymerization inhibitor (G) is 0.1% by mass or more and 5.0% by mass or less with respect to the total solid content of the photosensitive coloring composition for color filters. The photosensitive coloring composition for the above color filter.

<3> When the content of the phosphoric acid ester compound (H) having an ethylenically unsaturated group is 0.1% by mass or more and 5.0% by mass or less with respect to the total solid content in the photosensitive coloring composition for a color filter. Is there
The content of the amino group-containing resin (I) is 0.1% by mass or more and 5.0% by mass or less with respect to the total solid content of the photosensitive coloring composition for a color filter. thing.

<4> The photosensitive coloring composition for a color filter, which comprises an antioxidant (F) and a phosphoric acid ester compound (H) having an ethylenically unsaturated group.

<5> The photosensitive coloring composition for a color filter, wherein the antioxidant (F) is a phenolic antioxidant.

<6> The photosensitive coloring composition for a color filter, wherein the phosphoric acid ester compound (H) having an ethylenically unsaturated group is a phosphoric acid ester compound represented by the following general formula (1).
General formula (1)
[CH ₂ = CR ^1- CO-O-X ^1- O-CO-X ^2- O] _n- PO- (OR ² ) _m
In (formula (1), R ¹ and R ² are each independently hydrogen atom, and .X ¹ represents an aryl group which may have an alkyl group or a substituted group which may have a substituent X ² represents an alkylene group which may independently have a substituent. M represents an integer of 0 to 2, and n represents an integer of 1 to 3).

<7> A color filter comprising a filter segment formed from the above-mentioned photosensitive coloring composition for a color filter on a substrate.

The photosensitive coloring composition for a color filter of the present invention requires excellent high resolution as in the COA method, and the photosensitive coloring for a color filter having excellent adhesion that does not cause pattern peeling or pattern chipping. A composition and a color filter using the composition can be provided.

The photosensitive coloring composition for a color filter of the present invention includes a colorant (A), a resin (B) (excluding the resin (I)), a photopolymerizable monomer (C), and a photopolymerization initiator (D). ) And a photosensitive coloring composition for a color filter containing the solvent (E).
Further, it is composed of at least one selected from the group consisting of an antioxidant (F) and a polymerization inhibitor (G), a phosphoric acid ester compound (H) having an ethylenically unsaturated group, and an amino group-containing resin (I). Including at least one selected from the group,
The content of the colorant (A) is 25% by mass or more and 45% by mass or less with respect to the total solid content of the photosensitive coloring composition for a color filter, and the content of the photopolymerizable monomer (C) is It is characterized in that it is 30% by mass or more and 55% by mass or less with respect to the total solid content of the photosensitive coloring composition for a color filter.

Hereinafter, the present invention will be described in detail.
In the present application, when "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", or "(meth) acrylate" is described, unless otherwise specified, "(meth) acrylate" is used. It shall represent "acryloyl and / or methacrylic acid", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", or "acrylate and / or methacrylate". Further, "CI" mentioned in the present specification means a color index (CI).

<Colorant (A)>
The photosensitive coloring composition for a color filter of the present invention contains a colorant (A). The content of the colorant (A) is 25% by mass to 45% by mass with respect to the total solid content of the photosensitive coloring composition for a color filter. Within this range, sufficient color reproducibility can be obtained, preferably 30% by mass or more, and more preferably 35% by mass or more.
As the colorant, organic or inorganic pigments can be used alone or in combination of two or more. Among the pigments, pigments having high color development and high heat resistance are preferable, and organic pigments are usually used. Specific examples of organic pigments that can be used in the photosensitive coloring composition of the present invention are shown below by color index numbers. Further, as the colorant, a dye can be contained within a range that does not reduce the heat resistance.

Examples of the red pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Among these, azo pigments, diketopyrrolopyrrole-based, anthraquinone-based, quinophthalone-based, isoindoline-based, perinone-based, perylene-based, and benzimidazolone-based pigments can be mentioned from the viewpoint of lightness and coloring power. Specifically, C.I. I. Pigment Red 176, 177, 179, 254, 242, and naphthol azo pigments represented by the following general formula (2) are preferable.

General formula (2)

[In the general formula (2), A represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁷ or COOR ⁸ . R ² to R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon ^{atoms, -OR 9, -COOR 10, -CONHR} 11, -Represents NHCOR ¹² or SO ₂ NHR ¹³ . R ^{7 to} R ¹³ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like can be mentioned. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, more preferably C.I. I. Pigment Blue 15: 6. Further, the aluminum phthalocyanine pigments and the like described in JP-A-2004-333817, Patent No. 4893859 and the like can also be used, and the present invention is not particularly limited thereto.

Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 Can be mentioned. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Green 7, 36, 58, 59, 62, 63. Further, zinc phthalocyanine pigments and the like described in JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-070342 and the like can also be used, and the present invention is not particularly limited thereto.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,41,42,43,48,53,55,61,62,62: 1,63,65,73,74,75,81,83,87,93,94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, Examples thereof include 204, 205, 206, 207, 208, 231 and the quinophthalone compounds described in JP-A-2012-226110. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Yellow 138, 139, 150, 185, 231 and the quinophthalone compound described in JP-A-2012-226110.
Specific examples of the quinophthalone compound include, but are not limited to, the quinophthalone compounds (a) to (r) shown below.

Examples of the purple pigment include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

Examples of the orange pigment include C.I. I. Pigment Orange 38, 43, 64, 71, 73 and the like. Above all, from the viewpoint of brightness and coloring power, C.I. I. Pigment Oranges 38, 43 and 64 are preferred.

Examples of the black photosensitive coloring composition for forming the black matrix include carbon black, aniline black, anthraquinone-based black pigment, and perylene-based black pigment, specifically, C.I. I. Pigment Black 1, 6, 7, 12, 20, 31 and the like can be used. A mixture of a red pigment, a blue pigment, and a green pigment can also be used for the black photosensitive coloring composition. As the black pigment, carbon black is preferable from the viewpoint of price and light-shielding property, and carbon black may be surface-treated with a resin or the like. Further, in order to adjust the color tone, a blue pigment or a purple pigment can be used in combination with the black photosensitive coloring composition.

Inorganic pigments include barium sulfate, zinc flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, and titanium black. , Synthetic iron black, titanium oxide, metal oxide powder such as iron tetroxide, metal sulfide powder, metal powder and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness.

In the coloring composition of the present invention, a dye can also be used as a coloring agent. As the dye, any of acidic dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, medium dyes, construction dyes, sulfide dyes and the like can be used. Further, these derivatives or a lake pigment obtained by rake-forming the dye may be used.

The chemical structure of the dye includes, for example, azo dyes, azomethine dyes (Indian aniline dyes, Indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthra). Pyridone dyes, etc.), Carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acrydin dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes, etc. Dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo Examples thereof include dye structures derived from dyes selected from based dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and their metal complex dyes.

Among these dye structures, from the viewpoint of color characteristics such as hue, color separability, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and squaryliums. Dye structures derived from dyes selected from dyes selected from dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferable, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are preferable. A dye structure derived from a dye selected from the dyes is more preferable. For specific dye compounds that can form a dye structure, see "New Edition Dye Handbook" (Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colorists), "Dye Handbook" (Okawara et al.) Edited by Kodansha, 1986).

<Resin (B)>
The coloring composition for a color filter of the present invention contains a resin (B).
The resin (B) is for dispersing or permeating a pigment, and examples thereof include a thermoplastic resin and the like. The resin (B) is preferably a transparent resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. When used in the form of an alkali-developable photosensitive coloring composition, it is preferable to use an alkali-soluble vinyl-based resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic substituent. Further, in order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. , Polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin and the like.

Examples of the vinyl-based alkali-soluble resin obtained by copolymerizing the ethylenically unsaturated monomer containing an acidic substituent include a resin having an acidic substituent such as a carboxyl group and a sulfone group. Specifically, the alkali-soluble resin includes an acrylic resin having an acidic substituent, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, and an ethylene / (meth) acrylic acid copolymer. Alternatively, isobutylene / (anhydrous) maleic acid copolymer and the like can be mentioned. Among them, an acrylic resin having an acidic substituent and at least one resin selected from a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, are preferably used because they have high heat resistance and transparency. Be done.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin in which an ethylenically unsaturated double bond is introduced by the methods (i) and (ii) shown below.

[Method (i)]
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers is used. , The carboxyl group of the unsaturated monobasic acid having an ethylenically unsaturated double bond is added and reacted, and the generated hydroxyl group is further reacted with a polybasic acid anhydride to form an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce it.

Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. , And 3,4-epoxycyclohexyl (meth) acrylates, which may be used alone or in combination of two or more. From the viewpoint of reactivity with unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferable.

Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano-substituted products. Examples thereof include monocarboxylic acids, which may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. It doesn't matter. If necessary, such as by increasing the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride may be used to obtain the remaining anhydride. It is also possible to hydrolyze the group. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bond can be further increased.

As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with one or more other monomers. There is a method of adding an ethylenically unsaturated monomer having an epoxy group to a part of the carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and by copolymerizing with an unsaturated monobasic acid monomer having another carboxyl group or another monomer. There is a method of reacting the side chain hydroxyl group of the obtained copolymer with the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl methacrylates such as (meth) acrylates and cyclohexanedimethanol mono (meth) acrylates, which may be used alone or in combination of two or more. Further, a polyether mono (meth) acrylate obtained by superpolymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, poly γ-valerolactone, poly ε-caprolactone, and / or Polyester mono (meth) acrylate to which poly 12-hydroxystearic acid or the like is added can also be used. 2-Hydroxyethyl methacrylate or glycerol methacrylate is preferable from the viewpoint of suppressing foreign matter in the coating film.

Examples of the ethylenically unsaturated monomer having an isocyanate group include, but are not limited to, 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [methacryloyloxy] ethyl isocyanate, and the like. Two or more types can be used together.

In order to preferably disperse the pigment, the weight average molecular weight (Mw) of the resin (B) is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the Mw / Mn value is preferably 10 or less.

Further, from the viewpoint of pigment dispersibility, stability, developability, and heat resistance, a carboxyl group that acts as a pigment adsorbent group and an alkali-soluble group during development, an aliphatic group that acts as an affinity group for a pigment carrier and a solvent, and an aroma. The balance of group groups is important for pigment dispersibility, developer permeability in the coating film, developer solubility of uncured parts, and durability, and it is possible to use a resin having an acid value of 20 to 300 mgKOH / g. preferable. If the acid value is less than 20 mgKOH / g, the solubility in a developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, fine patterns may not remain.

Since the resin (B) has good film forming properties and various resistances, it is preferable to use the resin (B) in an amount of 30 parts by mass or more with respect to 100 parts by mass of the total weight of the colorant (A), and the pigment concentration is high. Since good color characteristics can be exhibited, it is preferable to use it in an amount of 500 parts by mass or less. More preferably 100 to 400 parts by mass. More preferably, it is 160 to 320 parts by mass. The chromaticity region can be expanded by the composition ratio of such a pigment.

<Photopolymerizable monomer (C)>
The photosensitive coloring composition for a color filter of the present invention contains a photopolymerizable monomer (C).
The photopolymerizable monomer includes a monomer or an oligomer that is cured by ultraviolet rays, heat, or the like to form a transparent resin. The content of the photopolymerizable monomer (C) is 30% by mass to 55% by mass with respect to the total solid content of the photosensitive coloring composition for a color filter. Within this range, a composition having high resolution and excellent pattern chipping and adhesion can be obtained. If it is less than 30% by mass, the resolution is poor, and if it exceeds 55% by mass, the pattern is chipped and peeled off. It is preferably 30 to 45%, more preferably 35 to 40%.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate ) Acrylate, Trimethylol Propane Tri (meth) Acrylate, Phenoxytetraethylene Glycol (Meta) Acrylate, Phenoxy Hexaethylene Glycol (Meta) Acrylate, Trimethylol Propane PO Modified Tri (Meta) Acrylate, Trimethylol Propane EO Modified Tri (Meta) Acrylate, EO-modified di (meth) acrylate of isocyanuric acid, EO-modified tri (meth) acrylate of isocyanuric acid, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6 -Hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate ) Acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, various acrylic acid esters such as methylolated melamine (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate, and methacrylate ester, (meth) acrylic acid , Styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, etc., but are not necessarily limited to these. It is not something that is done.
These photopolymerizable compounds may be used alone or in admixture of two or more at any ratio as required.

These commercially available products include KAYARAD R-128H, KAYARAD R526, KAYARAD PEG400DA, KAYARAD MAND, KAYAARD NPGADA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, KAYARAD R-551 -604, KAYARAD R-684, KAYARAD GPO-303, KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD DPHA-2C, KAYARAD D-310, KAYARAD D-330, KAYARAD DPCA-20 DPCA-60, KAYARAD DPCA-120, and M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360 manufactured by Toagosei Co., Ltd. , M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-221B, M -101A, Osaka Organic Co., Ltd. Viscort # 310HP, Viscort # 335HP, Viscort # 700, Viscort # 295, Viscort # 330, Viscort # 360, Viscort #GPT, Viscort # 400, Viscort # 405, Manufactured by Shin-Nakamura Chemical Co., Ltd. A-9300 and the like can be preferably used.

(Photopolymerizable monomer having an acid group)
The photopolymerizable monomer in the present invention may contain a photopolymerizable monomer having an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

Examples of the photopolymerizable monomer having an acid group include a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid, an esterified product of a dicarboxylic acid, and a polyvalent carboxylic acid. Examples thereof include esterified products with monohydroxyalkyl (meth) acrylates. Specific examples include monohydroxyoligoacrylates such as trimethylolpropane diacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 2-hydroxyethyl acrylate, 2- Examples thereof include monohydroxymonoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates, but the effects of the present invention are limited thereto. It is not something that is done.

As these commercially available products, Viscoat # 2500P manufactured by Osaka Organic Co., Ltd., M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toagosei Co., Ltd. and the like can be preferably used.

As the photopolymerizable monomer having these acid groups, one type can be used alone, or two or more types can be mixed at an arbitrary ratio as required.

(Photopolymerizable monomer having urethane bond)
The photopolymerizable monomer in the present invention may contain a photopolymerizable monomer containing at least one ethylenically unsaturated bond and one urethane bond. For example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting with a (meth) acrylate having a hydroxyl group. Urethane acrylate and the like can be mentioned.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylol propanetri (meth). Meta) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide-modified penta (meth) acrylate, dipentaerythritol propylene oxide-modified penta (meth) acrylate, dipentaerythritol caprolactone-modified penta (meth) acrylate, glycerol acrylate Examples thereof include methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy (meth) acrylate, and a hydroxyl group-containing polyol polyacrylate.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

Further, although the structure of the alcohol is not limited, it is preferable to use a polyhydric alcohol because the degree of cross-linking of the cured coating film is increased and the coating film resistance is increased. Examples of the polyhydric alcohol include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like.

As these commercially available products, DPHA-40HUX-5000, UX-5002D-M20, UX-5002D-P20, UX-5003D, UX-5005, etc. manufactured by Nippon Kayaku Co., Ltd. can be preferably used.

As these photopolymerizable monomers having a urethane bond, one type can be used alone, or two or more types can be mixed at an arbitrary ratio as required.

<Photopolymerization initiator (D)>
To the photosensitive composition of the present invention, a photopolymerization initiator is added to cure the composition by ultraviolet irradiation and a photopolymerization initiator is added to form a filter segment by a photolithography method. It can be prepared in the form of.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-. Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -Acetophenone compounds such as 4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one; benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4' -Methyldiphenyl sulfide, or benzophenone compounds such as 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 Thioxanthone compounds such as −diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6- Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4- Triazine compounds such as trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyl) Oxime)], or oxime ester compounds such as etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime); bis ( 2,4,6-trimethylbenzoyl) phenylphosphine oxide, or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, and ethylanthraquinone. Borate-based compounds; Carbazole-based compounds; Imidazole-based compounds; Alternatively, titanosen-based compounds and the like can be mentioned.

These photopolymerization initiators can be used alone or in admixture of two or more at any ratio as required.
As commercially available products, all acetophenone compounds are manufactured by BASF, "IRGACURE 907" (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one), "IRGACURE 369". (2- (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone), "IRGACURE 379" 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butane-1-one, as phosphine compounds, all manufactured by BASF, "IRGACURE 819" (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide), Examples thereof include "IRGACURE TPO" (2,4,6-trimethylbenzoyldiphenylphosphine oxide).

In the present invention, among these, it is preferable to contain an oxime ester compound.

(Oxime ester compound)
When an oxime ester compound absorbs ultraviolet rays, the NO bond of the oxime is cleaved to generate an iminyl radical and an alkyroxy radical. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the concentration of the colorant in the photosensitive coloring composition for a color filter is high, the ultraviolet transmittance of the coating film may be low and the curing degree of the coating film may be low, but the oxime ester compound is suitable because it has high quantum efficiency. Used for. More preferably, it is an oxime ester-based photopolymerization initiator represented by the general formula (3) or (4).

[Oxime ester-based photopolymerization initiator represented by the general formula (3)]
General formula (3)

In the general formula (3), Y ¹ and Y ² are each independently an alkyl group or an aryl group which may have a hydrogen atom or a substituent, and Y ⁴ and Y ⁶ are independent of each other. It is an alkyl group or an aryl group which may ^{have a hydrogen atom or a substituent, and Y 5} is an alkyl group, an aryl group or a Y which may have a hydrogen atom or a substituent. ^{It is a 7-} CO- group, and Y ⁷ is an alkyl group, an aryl group, or a heterocyclic group which may have a substituent.

Examples of the alkyl group in the general formula (3) include a linear, branched and cyclic alkyl group, and specifically, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, an n-butyl group and t. -Butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group and the like can be mentioned.
Examples of the aryl group in the general formula (3) include a phenyl group, a naphthyl group, an anthryl group and the like.
Examples of the heterocyclic group in the general formula (3) include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, and an isooxazole. Derived by removing hydrogen atoms from heterocycles such as rings, isothiazole rings, triazole rings, thiaziazole rings, oxazole rings, quinoline rings, benzofuran rings, indol rings, morpholine rings, pyrrolidine rings, piperidine rings, and tetrahydrofuran rings. There is a monovalent group.

Examples of the substituent which may be possessed include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group, a phenoxy group and a p-tolyloxy group. Aryloxy group, methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group and other alkoxycarbonyl groups, acetoxy group, propionyloxy group, benzoyloxy group and other acyloxy groups, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl. Acrylic groups such as groups and metoxaryl groups, alkylsulfanyl groups such as methylsulfanyl groups and tert-butylsulfanyl groups, arylsulfanyl groups such as phenylsulfanyl groups and p-tolylsulfonyl groups, alkylaminos such as methylamino groups and cyclohexylamino groups. Group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, arylamino group such as phenylamino group, p-tolylamino group, methyl group, ethyl group, tert-butyl group, dodecyl group, cyclopropyl Alkyl group such as group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, phenyl group, p-tolyl group, xsilyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group and the like. In addition to heterocyclic groups such as aryl group, fryl group and thienyl group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group and cyano group. , Trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumyl group, dimethylsulfoniumyl group, triphenylphenacylphosphoniumyl group and the like.
Further, one or more or one or more of these substituents may be present, and the hydrogen atom of these substituents may be further substituted with another substituent.

Y ¹ is preferably an aryl group that may have a substituent, Y ² is preferably an alkyl group having 1 to 20 carbon atoms that may have a substituent, and Y ⁴ and Y ⁶ are preferably hydrogen atom, the ^{Y 5} is preferably a hydrogen atom or ^Y 7 -CO- group.

Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (3) are photopolymerization initiators represented by the following chemical formulas (3-1) to (3-4).

[Oxime ester-based photopolymerization initiator represented by the general formula (4)]
General formula (4)

In the general formula (4), Z is a direct bond or a -CO- group.
Y ¹ and Y ² are alkyl groups or aryl groups that may independently have a hydrogen atom or a substituent, and Y ^{7 to Y 14} are independent hydrogen atoms or substituents, respectively. It is an alkyl group, an aryl group, a nitro group, or a Y ^15- CO- group which may have a group, and Y ¹⁵ is an alkyl group or an aryl group which may have a hydrogen atom or a substituent. Is.

The alkyl group and aryl group in the general formula (4) are synonymous with the alkyl group and aryl group in the general formula (3).

The substituent that may be possessed is synonymous with the substituent in the general formula (3).

Y ¹ is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, and Y ² is preferably an alkyl group or a substituent having 1 to 20 carbon atoms which may have a substituent. It is an aryl group which may have an aryl group, and Y ^{7 to Y 14} are independent of each other and may have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an aryl which may have a substituent. A group, a nitro group, or a Y ^15- CO- group, among which Y ^{7 to Y 9} , Y ^{10 to Y 12} and Y ¹³ are preferably hydrogen atoms, and Y ¹¹ is preferably a nitro group or Y ^15. -CO- group wherein more preferably ^Y 15 -CO- ^group, preferably a ^{Y 15} is an aryl group which may have a substituent.

When Z in the general formula (4) is a direct bond, an oxime ester-based photopolymerization initiator represented by the following general formula (4a) is preferable.

"Oxime ester-based photopolymerization initiator represented by the general formula (4a)"
General formula (4a)

The general formula (4a) corresponds to the case where Z in the general formula (4) is a direct bond and Y ³ is a monovalent organic group containing a carbazole group which may have a substituent, and is in the general formula (4). Y ^{7 to Y 10} and Y ^{12 to Y 13} are hydrogen atoms.
Further, Y ¹¹ is ^{preferably a Y 15-} CO- group or a nitro group. Y ¹⁵ is ^{synonymous with the substituents in Y 1} and Y ² , and is preferably an aryl group which may have a substituent. The Y ^15- CO- group is preferably an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, or a metoxalyl group which may further have a substituent. More preferably, it is a benzoyl group or a nitro group which may have a substituent. As Y ¹⁴ , an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group which may have a substituent is preferable.

Further, as the substituent in the benzoyl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms or an alkyloxy group is preferable. Further, as the alkyl group, a methyl group and an ethyl group are preferable, and among the alkyloxy groups, a linear group having 2 to 18 carbon atoms and optionally having one or more −O− interrupted, a linear group or a branched chain group. monocyclic or fused polycyclic alkyl group is preferable, if a carbon number of 2 in the Y ¹ 18 by linear interrupted by one or more -O-, branched, monocyclic or fused polycyclic Synonymous with alkyloxy group.

Y ² is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, and is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. It is a cycloalkyl group such as a cyclooctadecyl group. Further, an aryl group which may have a substituent is preferable, and an alkyl group having 1 to 20 carbon atoms which may further have a substituent, or a methoxy group, an ethoxy group, or a tert-butoxy group is preferable as the substituent. Alkoxy groups such as are preferable.

Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (4a) are photopolymerization initiators represented by the following chemical formulas (4a-1) to (4a-6).

"Oxime ester-based photopolymerization initiator represented by the general formula (4b)"
When Z in the general formula (4) is a -CO- group, an oxime ester-based photopolymerization initiator represented by the following general formula (4b) is preferable.

General formula (4b)

Formula (4) is, Z in the general formula (4) is -CO- group, Y ³ corresponds to the case of the monovalent organic group containing a good carbazole group which may have a substituent group, the keto form carbazole group It is an oxime ester-based photopolymerization initiator having the above.
Y ^{7 to Y 13} are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a ^{substituent, and Y 14} may have a substituent. It is preferably a good aryl group.
As the substituent of the aryl group which may have a substituent, an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group and a metoxalyl group is preferable, and a benzoyl group is more preferable.

Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (4b) are photopolymerization initiators represented by the following chemical formulas (4b-1) to (4b-4).

Commercially available products of these oxime ester compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IRGACURE OXE-01) and etanone from BASF. , 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02), N-1919 (manufactured by ADEKA), TRONLY TR-PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all manufactured by Joshu Strong New Materials Co., Ltd.) and the like are commercially available. In addition, the oximes described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-0372223, JP-A-2010-215575, JP-A-2011-02998, etc. It is also possible to use an ester-based photopolymerization initiator.

The content of the oxime ester compound is preferably 2 to 50 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 2 to 30 parts by mass from the viewpoint of photocurability and developability. If it is less than 2 parts by mass, the adhesion of the formed pattern to the substrate may be deteriorated, and if it exceeds 50 parts by mass, a problem may occur in developability or a decrease in brightness after heat treatment at 230 ° C. may occur.

<Sensitizer>
Further, the photosensitive composition of the present invention may contain a sensitizer.
Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, acrydin derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, Azulene derivative, azulenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglycolate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4,4'- Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-bis (diethylamino) benzophenone.

Among the above sensitizers, examples of the sensitizer that can be particularly preferably sensitized include a thioxanthone derivative, a Michler ketone derivative, and a carbazole derivative. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.
These sensitizers can be used alone or in admixture of two or more at any ratio, if necessary.

Examples of commercially available products include "KAYACURE DETX-S" (2,3-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.) and "EAB-F" (4,4'-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Industry Co., Ltd.). Be done.

More specifically, Okawara Nobu et al., "Dye Handbook" (1986, Kodansha), Okawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " Examples thereof include, but are not limited to, the sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

The content of the sensitizer when used is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the photoradical polymerization initiator contained in the coloring composition, from the viewpoint of photocurability and developability. More preferably, it is 5 to 50 parts by mass.

<UV absorber>
The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples thereof include a benzotriazole-based organic compound, a triazine-based organic compound, a benzophenone-based organic compound, a cyanoacrylate-based organic compound, and a salicylate-based organic compound. ..

The content of the ultraviolet absorber is preferably 5 to 70% by mass based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. If the content of the ultraviolet absorber is less than the above, the effect of the ultraviolet absorber is small and the resolution cannot be ensured, and if it is more than the above, the sensitivity becomes low and the pixel peeling and the hole diameter are larger than the design value. There may be a problem such as becoming.

At this time, when the photosensitive coloring composition for a color filter contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the solid content of the photosensitive coloring composition for a color filter. If the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above, the adhesion is weakened and pixel peeling occurs, and if it is more than the above, the sensitivity may be too high and the resolution may be deteriorated.

At this time, when the photosensitive coloring composition for a color filter contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

Examples of the benzotriazole-based organic compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, and octyl-3 [3-tert-butyl. -4-Hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H) -Phenyl-benzotriazole-2-yl) phenyl] propionate mixture, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-t butyl- 5-Methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t- Octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H-benzotriazole-2-yl)-(1,1-dimethylethyl) -4- Hydroxy, C7-9 side chain and linear alkyl ester compounds, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-) Benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol.

More specifically, BASF's "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN 326", "TINUVIN 328", "TINUVIN 329", "TINUVIN 360", " "TINUVIN 384-2", "TINUVIN 900", "TINUVIN 928", "TINUVIN 99-2", "TINUVIN 1130", "ADEKA STAB LA-29" manufactured by ADEKA, "RUNA-93" manufactured by Otsuka Chemical Co., Ltd., etc. Be done.

Examples of the triazine-based organic compound include 2- [4,6-di (2,4-kisilyl) -1,3,5-triazine-2-yl] -5-octyloxyphenol, 2- [4,6-bis. (2,4-Dimethylphenyl) -1,3,5-triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl)- Reaction product of 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl-glycidate ester, 2,4-bis "2-hydroxy-4-butoxyphenyl" -6- (2,4-dibutoxyphenyl) -1,3-5-triazine and the like can be mentioned.

More specifically, "KEMISORB 102" manufactured by Chemipro Kasei Co., Ltd., "TINUVIN 400", "TINUVIN 405", "TINUVIN 460", "TINUVIN 477-DW", "TINUVIN 479", "TINUVIN 1577", manufactured by BASF Corporation, Examples thereof include "ADEKA STAB LA-46" and "ADEKA STAB LA-F70" manufactured by ADEKA, and "CYASORB UV-1164" manufactured by Sun Chemical.

Examples of benzophenone-based organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid-3 water temperature, and 2-hydroxy-4-n-. Examples thereof include octoxybenzophenone and 2,2-di-hydroxy-4-methoxybenzophenone.

More specifically, "KEMISORB 10", "KEMISORB 11", "KEMISORB 11S", "KEMISORB 12", "KEMISORB 111" manufactured by Chemipro Kasei Co., Ltd., "SEESORB 101", "SEESORB 107", ADEKA manufactured by Cypro Kasei Co., Ltd. Examples thereof include "ADEKA STAB 1413" manufactured by the company.

<Thiol chain transfer agent>
The photosensitive composition of the present invention may contain a thiol-based chain transfer agent as the chain transfer agent. By using thiol together with a photopolymerization initiator, a chain transfer agent acts as a chain transfer agent in the radical polymerization process after light irradiation, and chile radicals that are less susceptible to polymerization inhibition by oxygen are generated, so that the obtained photosensitive composition has high sensitivity. Become.

Further, a polyfunctional aliphatic thiol bonded to an aliphatic group such as methylene or ethylene group having two or more SH groups is preferable. More preferably, it is a polyfunctional aliphatic thiol having 4 or more SH groups. By increasing the number of functional groups, the polymerization initiation function is improved, and the pattern can be cured from the surface to the vicinity of the substrate.

Examples of the polyfunctional thiol include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropio. Nate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetraxthioglycolate, pentaerythritol tetraxthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s- Examples thereof include triazine, and preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

These thiol-based chain transfer agents may be used alone or in admixture of two or more.

The content of the thiol-based chain transfer agent is preferably 1 to 10% by mass, more preferably 2.0 to 8.0% by mass, based on the total solid content of the photosensitive composition. In this range, the effect of the chain transfer agent is increased, and the sensitivity, taper shape, wrinkles, film shrinkage rate, etc. are improved.

<Solvent (E)>
The photosensitive composition for a color filter of the present invention contains a solvent (E).
It is easy to sufficiently disperse and permeate the colorant in the colorant carrier with a solvent and apply it on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form a color film. can do. Of these, an organic solvent is preferable. The organic solvent is selected in consideration of the good coatability of the photosensitive composition, the solubility of each component of the photosensitive composition, and the safety.

Examples of the organic solvent include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1 , 4-Butandiol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5 -Trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3 -Methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate , N-Methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, Isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene Glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether Acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glyco Lumethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, Propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether pro Examples thereof include propyleneate, benzyl alcohol, methylisobutylketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate and dibasic acid ester.
These solvents can be used alone or in admixture of two or more in any ratio as required.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, and ethylene glycol monomethyl ether are good because of the good dispersibility and permeability of the colorant and the coatability of the photosensitive composition. Acetates such as acetate, ethylene glycol monoethyl ether acetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, 1,4-butanediol diacetate, butanediol diacetate, benzyl alcohol, diacetone alcohol, 1-methoxy It is preferable to use alcohols such as -2-propanol and 3-methoxybutanol, ketones such as cyclohexanone, ethyl 3-ethoxypropionate, and the like.

Further, the organic solvent is used in an amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the colorant because the photosensitive composition can be adjusted to an appropriate viscosity and a colored film having a desired uniform film thickness can be formed. Is preferable.

<At least one selected from the group consisting of the antioxidant (F) and the polymerization inhibitor (G)>
The photosensitive coloring composition for a color filter of the present invention contains at least one selected from the group consisting of an antioxidant (F) and a polymerization inhibitor (G), so that pattern peeling and pattern chipping do not occur. A composition having excellent adhesion can be obtained.
The antioxidant (F) and the polymerization inhibitor (G) will be described in detail below.

<Antioxidant (F)>
The "antioxidant" in the present invention may be a compound having an ultraviolet absorption function, a radical capture function, or a peroxide decomposition function. Specifically, the antioxidant is a hindered phenol-based or a hindered amine-based compound. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, sulcylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Further, the antioxidant used in the present invention preferably does not contain a halogen atom.

Among these antioxidants, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, the ones preferable are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Agents can be mentioned.

Examples of the hindered phenolic antioxidant include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), and the like. 1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di) -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-thio- Bis- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) )-Propionate, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -butane, 2,2'-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro) Phenol) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.
Specific examples include Adecastab AO-20, AO-30, AO-40, AO50, AO60, AO80, AO320 manufactured by ADEKA Co., Ltd., KEMINOX101 179, 76, 9425 manufactured by Chemipro Co., Ltd., IRGANOX1010, 1035 manufactured by BASF Co., Ltd. Examples thereof include 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, and Sianox CY-1790 and CY-2777 manufactured by Sun Chemical Co., Ltd.

Examples of hindered amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate. N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4) -Piperidyl) Amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3) 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6) -Tetramethyl-4-piperidyl) imino} Hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazin-2,4) -Diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-Hydroxyethyl) -4-hydroxy-2,2,6,6-polycondensate with tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazine-2-yl] -4,7-diazadecan-1,10-diamine and the like. In addition, oligomer-type and polymer-type compounds having a hindered amine structure can also be used.
Specific examples include ADEKASTUB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, manufactured by ADEKA Co., Ltd. LA-402F, LA-502XP, KAMISTAB29, 62, 77, 29, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin249, TINUVIN111FDL, 123, 144, 292, 5100 manufactured by BASF Co., Ltd., Siasorb UV-3346, UV manufactured by Sun Chemical Co., Ltd. -3259, UV-3853 and the like can be mentioned.

Phenyl antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecyl. Phosphite, Diphenyltridecylphosphite, Triphenylphosphite, Tris (nonylphenyl) phosphite, 4,4'isopropyridene diphenolalkylphosphite, trisnonylphenylphosphite, trisdinonylphenylphosphite, tris (2) , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonyl) Phenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butanetriphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis (4-t-butylphenyl) Phosphite, Sodium-2,2-Methylene-bis (4,6-di-t-butylphenyl) -Phosphite, 1,3-bis (diphenoxyphosphonyloxy) -benzene, ethylbis phosphite (2, 4-Ditert-butyl-6-methylphenyl) and the like. In addition, oligomer-type and polymer-type compounds having a phosphite structure can also be used.
Specific examples include ADEKA Corporation ADEKA STAB PEP-36, PEP-8, HP-10, ADEKA STAB 2112, 1178, 1500, C, 3013, TPP, BASF Corporation IRGAFOS168, Clariant Chemicals Corporation Hostanox P-EPQ, etc. Can be mentioned.

Examples of sulfur-based antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 2,4-bis [(octylthio) methyl]-. o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (Dodecylthio) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like. In addition, oligomer-type and polymer-type compounds having a thioether structure can also be used.
Specific examples include ADEKA STAB AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Kasei Co., Ltd.

As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.
Specific examples include ADEKA Corporation LA-29, LA-31RG, LA-32, LA-36, -412S, CHEMIPRO KASEI Co., Ltd. KEMISORB71, 73, 74, 79, 279, and BASF Corporation TINUVIN PS. , 99-2, 384-2, 900, 928, 1130 and the like.

Examples of benzophenone-based antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, and 2-hydroxy-4. -Octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4 Examples thereof include −methoxy-5 sulfobenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. In addition, oligomer-type and polymer-type compounds having a benzophenone structure can also be used.
Specific examples include ADEKA TAB 1413 manufactured by ADEKA Corporation, KEMISORB10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., UV-12 manufactured by Sun Chemical Co., Ltd., UV-329, and the like.

Examples of the triazine-based antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.
Specific examples include ADEKA Corporation LA-46, F70, KEMISORB102 manufactured by ChemiPro Kasei Co., Ltd., TINUVIN400, 405, 460, 477, 479 manufactured by BASF Co., Ltd., Siasorb UV-1164 manufactured by Sun Chemical Co., Ltd., and the like. ..

Examples of the salicylic acid ester-based antioxidant include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate. In addition, oligomer-type and polymer-type compounds having a sulcylic acid ester structure can also be used.

These antioxidants can be used alone or in admixture of two or more at any ratio as required. Among the antioxidants, the contact holes are less likely to be closed by increasing the amount of the initiator, and radicals. A hindered phenolic antioxidant that can more capture the above is most preferable.

The total content of the antioxidant (F) and the polymerization inhibitor (G) described later is preferably 0.1 to 5.0% by mass with respect to the total solid content of the photosensitive coloring composition. Within this range, the pattern linearity is excellent and the pattern is not chipped. More preferably, it is 1.0 to 3.0% by mass.
The photosensitive coloring composition for a color filter of the present invention contains at least one selected from the group consisting of an antioxidant (F) and a polymerization inhibitor (G), but at least contains an antioxidant (F). Is preferable from the viewpoint of pattern linearity.

<Polymerization inhibitor (G)>
The photosensitive coloring composition for a color filter of the present invention may contain a polymerization inhibitor in order to prevent the mask from being exposed to light by diffracted light during exposure. By adding a polymerization inhibitor, it is possible to obtain the effect of preventing the curing from proceeding outside the desired pattern by chain polymerization by photosensitization.

Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, and 2-propylcatechol. , 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert- Alkyl catechol compounds such as butyl catechol, 3,5-di-tert-butyl catechol, 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, Alkyl resorcinol compounds such as 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2, Alkylhydroquinone compounds such as 5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, phosphines such as trioctylphosphine oxide and triphenylphosphine oxide. Examples thereof include phosphite compounds such as oxide compounds, triphenylphosphite and trisnonylphenylphosphite, pyrogallol and fluoroglucin.

As described above, the total content of the antioxidant (F) and the polymerization inhibitor (G) described later is 0.1 to 5.0% by mass with respect to the total solid content of the photosensitive coloring composition. Is preferable. Within this range, the pattern linearity is excellent and the pattern is not chipped. More preferably, it is 1.0 to 3.0% by mass.

<At least one selected from the group consisting of the phosphate ester compound (H) having an ethylenically unsaturated group and the amino group-containing resin (I)>
The photosensitive coloring composition for a color filter of the present invention contains at least one selected from the group consisting of a phosphoric acid ester compound (H) having an ethylenically unsaturated group and an amino group-containing resin (I). A composition having excellent adhesion can be obtained without causing pattern peeling or pattern chipping.
The phosphoric acid ester compound (H) having an ethylenically unsaturated group and the amino group-containing resin (I) will be described in detail below.

<Phosphate ester compound (H) having an ethylenically unsaturated group>
In the present invention, since the phosphoric acid ester has an ethylenically unsaturated group, even if the obtained photosensitive resin composition is cured by heat or light, the phosphoric acid ester does not bleed out and defects occur in the liquid crystal panel. Suppress.
The phosphoric acid ester (H) having an ethylenically unsaturated group is a (meth) acrylate or an allyl compound having a phosphoric acid ester group, and specifically, 2- (meth) acryloyloxyethyl acid phosphate or di-. 2- (Meta) acryloyloxyethyl phosphate, ethylene oxide-modified dimethacrylate phosphate, 3- (meth) acryloyloxypropyl acid phosphate, di-3- (meth) acryloyloxypropyl acid phosphate, diphenyl (2-acryloyloxy) Ethyl) phosphate, diphenyl (2-methacryloyloxyethyl) phosphate, phenyl (2-acryloyloxyethyl) phosphate, metachloroyl-oxyethyl acid phosphate monoethanolamine salt, 3-chloro-2-acid phosphooxypropyl methacrylate, acid phospho Oxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol methacrylate, (meth) acryloyloxy-2-hydroxypropyl acid phosphate, (meth) acryloyloxy-3-hydroxypropyl acid phosphate, (meth) acryloyloxy-3 -Chloro-2-hydroxypropyl acid phosphate, 2-metacloyloxyethyl acid phosphate, allyl alcohol acid phosphate and the like can be mentioned.

Commercially available products of these compounds include JPA-514 (manufactured by Johoku Chemical Industry Co., Ltd.), light acrylate P-1A (N), P-1M, P-2M (manufactured by Kyoeisha Chemical Co., Ltd.), KAYAMER PM-2, PM-21. (Manufactured by Nippon Kayaku Co., Ltd.), MR-200, MR-260 (manufactured by Daihachi Chemical Industry Co., Ltd.) and the like.

Among them, in consideration of compatibility with the alkali-soluble resin, a phosphoric acid ester compound containing ethylenically unsaturated represented by the following general formula (1) is preferable, and one type may be used alone or two or more types may be combined. May be used.
General formula (1)
[CH ₂ = CR ^1- CO-O-X ^1- O-CO-X ^2- O] _n- PO- (OR ² ) _m
In (formula (1), R ¹ and R ² are each independently hydrogen atom, and .X ¹ represents an aryl group which may have an alkyl group or a substituted group which may have a substituent X ² represents an alkylene group which may independently have a substituent. M represents an integer of 0 to 2, and n represents an integer of 1 to 3).

Examples of the ^{alkyl group which may have a substituent in R 1} and R ² include a linear, branched and cyclic alkyl group, and specifically, a methyl group, an ethyl group, a normal propyl group and an isopropyl. Examples thereof include a group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group and a hexadecyl group.

Examples of the aryl group which may have a substituent in R ¹ and R ² include a phenyl group, a naphthyl group, an anthryl group and the like.

Examples of the alkylene group which may have a substituent in X ¹ and X ² include a linear, branched and cyclic alkylene group, and specifically, a methylene group, an ethylene group, an isoprolene group and a cyclohexylene group. Examples include groups, n-octyl groups, hexadecyl groups and the like.

X ¹ is preferably an unsubstituted alkylene group, more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably an ethylene group.

The X ^2, is preferably an unsubstituted alkylene group, more preferably an alkylene group having 3 to 10 carbon atoms, particularly preferably _-C 5 _{H 10} - is.

The substituent that may be possessed is synonymous with the substituent in the general formula (3).

The phosphoric acid ester compound containing ethylenically unsaturated represented by the general formula (1) is preferably ethylene oxide-modified dimethacrylate phosphate.

The content of the phosphoric acid ester compound (H) having an ethylenically unsaturated group is preferably 0.1 to 5.0% by mass with respect to the total solid content of the photosensitive coloring composition. Within this range, the adhesion is excellent and the pattern does not peel off. More preferably, it is 0.5 to 2.0% by mass.
The photosensitive coloring composition for a color filter of the present invention contains at least one selected from the group consisting of a phosphoric acid ester compound (H) having an ethylenically unsaturated group and an amino group-containing resin (I), but at least. It is preferable to contain a phosphoric acid ester compound (H) having an ethylenically unsaturated group from the viewpoint of adhesion.

<Amino group-containing resin (I)>
Since the amino group-containing resin (I) has a portion that interacts with the substrate to be coated, the adhesion is improved during the production of the color filter and the pattern peeling is eliminated. Specifically, the amino group-containing resin (I) includes polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acids. Alkylamine salts and long-chain polyaminoamide phosphates are used, and these can be used alone or in admixture of two or more, but are not necessarily limited to these.

Commercially available amino group-containing resins include Dsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, 21116 or Lactimon, Lactimon-WS or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000 , 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, manufactured by BASF Japan. 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. , PB824 and the like.

The content of the amino group-containing resin (I) is preferably 0.1 to 5.0% by mass with respect to the total solid content of the photosensitive coloring composition. Within this range, the adhesion is excellent and the pattern does not peel off. It is 0.5 to 2.0% by mass.

<Thermosetting agent>
In the present invention, a thermosetting compound may be further contained in combination with a thermoplastic resin which is a resin.
Thermosetting compounds include, for example, epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins. Examples include, but are not limited to, urea compounds and / or resins, phenolic compounds and / or resins.

<Leveling agent>
It is preferable to add a leveling agent to the coloring composition for a color filter of the present invention in order to improve the leveling property of the composition on a transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning Co., Ltd. and BYK-333 manufactured by Big Chemie Co., Ltd. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by mass based on 100% by mass of the total mass of the coloring composition.

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, the same. It is useful to have a feature of low surface tension lowering ability and good wettability to a glass plate despite having low surface tension lowering ability, and in an addition amount in which defects of the coating film due to foaming do not appear. Those capable of sufficiently suppressing chargeability can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are alternately and repeatedly bonded. Didimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. 2207, but is not limited to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Esther and the like can be mentioned.

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based and silicone-based surfactants.

<Other ingredients>
The coloring composition for a color filter of the present invention contains an adhesion improver such as a silane coupling agent in order to enhance the adhesion to a transparent substrate, or an amine compound having a function of reducing dissolved oxygen. Can be made to.

Examples of the silane coupling agent include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β-(. 3,4-Epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy) Epoxysilanes such as cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ Examples thereof include aminosilanes such as −aminopropyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

The silane coupling agent can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant in the coloring composition.

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -Dimethylaminobenzoate 2-ethylhexyl, N, N-dimethylparatoluidine and the like can be mentioned.

<Manufacturing method of photosensitive coloring composition for color filter>
The photosensitive coloring composition for a color filter of the present invention contains a colorant (A) in a colorant carrier such as a resin (B) and / or a solvent, preferably a dispersion aid, in a kneader, two roll mills. , A three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, or an attritor can be used to finely disperse and produce (colorant dispersion). At this time, two or more kinds of colorants and the like may be dispersed in the colorant carrier at the same time, or those dispersed separately in the colorant carrier may be mixed.
If the colorant such as a dye is highly soluble, specifically, if it is highly soluble in the solvent used, dissolved by stirring, and no foreign matter is confirmed, it is manufactured by finely dispersing as described above. No need.

When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent-developing type or alkali-developing type coloring composition. The solvent-developed or alkaline-developed coloring composition includes the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Dispersion aid>
When the colorant is dispersed in the colorant carrier, a dispersion aid such as a resin-type dispersant, a dye derivative, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing the reaggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has high lightness and viscosity stability. Become good.

[Resin type dispersant]
The resin-type dispersant has a colorant-affinitive portion having a property of adsorbing to the additive colorant and a portion compatible with the colorant carrier, and is adsorbed on the additive colorant and dispersed on the colorant carrier. It works to stabilize. Specifically, as the resin type dispersant, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products of these, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group. Oily dispersants such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resins, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphoric acid ester-based, etc. are used, and these can be used alone or in admixture of two or more. However, it is not necessarily limited to these.

The dispersant used in the present invention is preferably a polymer dispersant having a basic functional group, such as a nitrogen atom-containing graft copolymer, a tertiary amino group in the side chain, a quaternary ammonium base, or a nitrogen-containing heterocycle. A nitrogen atom-containing acrylic block copolymer and a urethane-based polymer dispersant having a functional group containing the above are preferable. The resin type dispersant is preferably used in an amount of about 5 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the colorant.

The basic resin-type dispersant having an amino group corresponds to the above-mentioned amino group-containing resin (I).

Further, the resin type dispersant used in the present invention preferably contains the following (S1) or (S2) as a resin type dispersant having a carboxyl group.
(S1) A resin-type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride.
(S2) A weight obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride. A resin-type dispersant that is a coalescence.

≪Resin type dispersant (S1) ≫
The resin-type dispersant (S1) can be produced by a known method such as WO2008 / 007776, Japanese Patent Application Laid-Open No. 2008-029901, and Japanese Patent Application Laid-Open No. 2009-155406. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, the ethylenically unsaturated monomer (r) is polymerized in the presence of the compound (q) having a hydroxyl group. It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since the number of terminal hydroxyl groups is preferably plural, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a more preferable example, a polymer having two hydroxyl groups at one end contains a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (p1) obtained by polymerizing the ethylenically unsaturated monomer (r) contained therein. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride to form an ester bond, while the anhydrous ring is opened and the carboxylic acid. Produces.

≪Resin type dispersant (S2) ≫
The resin-type dispersant (S2) can be produced by a known method such as JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, and for example, a compound having a hydroxyl group. By polymerizing the ethylenically unsaturated monomer (r) in the presence of a reaction product of the hydroxyl group of (q) and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. can get. Above all, in the presence of a reaction product of the hydroxyl group of the compound (q1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. It is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing the monomer (r1).

The difference between (S1) and (S2) is whether the introduction of the polymer moiety obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or later. The molecular weight and the like may differ slightly depending on various conditions, but theoretically the same can be obtained if the reaction conditions are the same as those of the raw material.

[Dye derivative]
As the dye derivative used in the present invention, a known dye derivative having an acidic group, a basic group, a neutral group or the like in the organic dye residue can be used. For example, compounds having acidic functional groups such as sulfo group, carboxy group and phosphoric acid group and amine salts thereof, compounds having basic functional groups such as sulfonamide group and tertiary amino group at the terminal, phenyl group and phthalimide. Examples thereof include compounds having a neutral functional group such as an alkyl group. Japanese Patent Application Laid-Open No. 63-305173, Japanese Patent Application Laid-Open No. 57-15620, Japanese Patent Application Laid-Open No. 59-40172, Japanese Patent Application Laid-Open No. 63-17102, Japanese Patent Application Laid-Open No. 5-9469, Japanese Patent Application Laid-Open No. 2001-335717, Japanese Patent Application Laid-Open No. 63-305173 Kai 2003-128669, JP2004-091497, 2007-156395, 2008-094873, 2008-094986, 2008-095007, 2008 -195916, Japanese Patent No. 4585781, Japanese Patent Application Laid-Open No. 2006-291194, Japanese Patent Application Laid-Open No. 2007-226161, Japanese Patent Application Laid-Open No. 2007-314681, Japanese Patent Application Laid-Open No. 2007-314785, Japanese Patent Application Laid-Open No. 2012-226110. , Japanese Patent Application Laid-Open No. 2017-165820, Japanese Patent Application Laid-Open No. 2005-181383, and the like. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group, a basic group, a neutral group, or the like. A compound having a functional group of is synonymous with a dye derivative. In addition, these can be used alone or in combination of two or more.

From the viewpoint of improving dispersibility, the content of the dye derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more with respect to 100 parts by mass of the colorant. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by mass or less, more preferably 35 parts by mass or less.

[Surfactant]
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate. , Anionic surfactants such as monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazolin, which may be used alone or in combination of two or more. They can be mixed and used, but are not necessarily limited to these.

When a surfactant is added, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. If the content of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the effect of addition, and if the content is more than 55 parts by mass, the dispersion may be affected by the excess dispersant. ..

<Removal of coarse particles>
The colored composition of the present invention comprises coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, and coarse particles of 5 μm or more, preferably coarse particles of 0.5 μm or more, by means such as centrifugation, filtration with a sintering filter or a membrane filter. It is preferable to remove the mixed dust. As described above, it is preferable that the coloring composition does not substantially contain particles having a size of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
The color filter of the present invention is a color filter including at least one filter segment formed by the coloring composition for a color filter of the present invention.
The color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one filter segment provides the coloring composition for a color filter of the present invention. It is preferably formed using.

<Manufacturing method of color filter>
The color filter of the present invention can be produced by a photolithography method using a coloring composition for a color filter.
Specifically, for example, in the method for producing a color filter according to the following steps (i), (ii), (iii) and (iv), the following coloring composition for a color filter is a colorant (A) and a resin. A photosensitive coloring composition for a color filter containing (B), a photopolymerizable monomer (C), a photopolymerization initiator (D) and a solvent (E), further comprising an antioxidant (F) and polymerization. At least one selected from the group consisting of the banning agent (G) and at least one selected from the group consisting of the phosphoric acid ester compound (H) having an ethylenically unsaturated group and the amino group-containing resin (I). The content of the content-containing colorant (A) is 25% by mass to 45% by mass with respect to the total solid content of the photosensitive coloring composition for a color filter, and the content of the photopolymerizable monomer (C) is It can be produced by a method for producing a color filter, which comprises 30% by mass to 55% by mass with respect to the total solid content of the photosensitive coloring composition for a color filter.
<Process>
(I): Step of obtaining a coating film by applying a coloring composition for a color filter on a substrate (ii): After step (i), a step of exposing the coating film with ultraviolet rays through a mask (iii): After step (ii), a pattern is obtained by developing the exposed coating film with an alkaline developer. Step (iv): After step (iii), a step of post-baking the pattern.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively. Further, "PGMAC" means propylene glycol monomethyl ether acetate.

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin is polystyrene-equivalent measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120 GPC) equipped with an RI detector and using THF as a developing solvent. Weight average molecular weight (Mw).

<Manufacturing method of resin solution>
(Resin solution (B-1))
100 parts of propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable 4-neck flask, and heated to 120 ° C. while injecting nitrogen gas into the vessel. At temperature, 16.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage. The mixture was added dropwise over 2.5 hours to carry out a polymerization reaction.
Next, the inside of the flask was replaced with air, and 17.0 parts of acrylic acid and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, and the temperature was 120 ° C. The reaction was carried out for 5 hours to obtain a resin solution having a weight average molecular weight of about 12,000. Since the added acrylic acid ester-bonds to the epoxy group terminal of the glycidyl methacrylate structural unit, no carboxyl group is generated in the resin structure.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of the two carboxyl groups generated by cleavage of the carboxylic acid anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal, and the weight average molecular weight is about 13. A resin solution of 000 was obtained.
Propylene glycol monomethyl ether acetate was added so that the non-volatile content was 20% to obtain a resin solution (B-1).

The weight ratio of the constituent units in the resin solution (B-1) was tetrahydrophthalic anhydride; 22.0% by mass, styrene; 15.0% by mass, dicyclopentanyl methacrylate; 29.3% by mass, glycidyl as the constituent units. The total amount of methacrylate and acrylic acid ester-bonded to the glycidyl terminal thereof; 37.4% by mass.

(Resin solution (B-2))
70.0 parts of propylene glycol monoethyl ether acetate was placed in a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, and the temperature was raised to 80 ° C., and the inside of the reaction vessel was filled with nitrogen. After substitution, 3.8 parts of methacrylic acid, 4.1 parts of 2-hydroxyethyl methacrylate, 7.4 parts of benzyl methacrylate from the dropping tube, paracumylphenol ethylene oxide-modified acrylate (Aronix M- manufactured by Toa Synthetic Co., Ltd.) 110 ") A mixture of 7.4 parts and 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of acrylic resin having a weight average molecular weight of 30,000.
After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol mono is added so that the non-volatile content is 20% by mass in the previously synthesized resin solution. Ethyl ether acetate was added to obtain a resin solution (B-2), which is an alkali-soluble resin.

(Resin solution (B-3))
100 parts of propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable 4-neck flask, and heated to 120 ° C. while injecting nitrogen gas into the vessel. At temperature, 74.6 parts of benzyl methacrylate, 28.3 parts of acrylic acid, 18.3 parts of dicyclopentanyl methacrylate, and azobisisobutyronitrile 1.0 as a catalyst required for the reaction of the precursor at this stage. The mixture of parts was added dropwise over 2.5 hours to carry out a polymerization reaction.
Next, the inside of the flask was replaced with air, and 19.7 parts of glycidyl methacrylate and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, and the temperature was 120 ° C. The reaction was carried out for 5 hours to obtain a resin solution having a weight average molecular weight of about 12,500.
Propylene glycol monomethyl ether acetate was added so that the non-volatile content was 20% to obtain a resin solution (B-3).
The weight ratio of the constituent units in the resin solution (B-3) was acrylic acid; 13.0% by mass, benzyl methacrylate; 53.0% by mass, dicyclopentanyl methacrylate; 13% by mass, and ester-bonded to the acrylic acid terminal. Glysidyl methacrylate; 21.0% by mass.

(Resin solution (B-4))
A flask equipped with a cooling tube and a stirrer was charged with 3 parts of 2,2'-azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate, followed by 1,2,2,6,6-pentamethylpiperidyl methacrylate 1. , 15 parts methacrylic acid, 34 parts 2-hydroxyethyl methacrylate, 20 parts N-phenylmaleimide, 15 parts styrene, 10 parts benzyl methacrylate, 5 parts n-butyl methacrylate and 2,4-diphenyl-4- as a molecular weight regulator. 5 parts of methyl-1-pentene (trade name: Nofmer MSD manufactured by Nippon Oil & Fat Co., Ltd.) was charged and substituted with nitrogen. Then, the reaction solution was gently stirred to raise the temperature of the reaction solution to 80 ° C., and the temperature was maintained for 5 hours for polymerization to obtain an acrylic resin solution having a weight average molecular weight of 12,500. After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl is prepared so that the non-volatile content is 20% by mass in the previously synthesized resin solution. Ether acetate was added to obtain a resin solution (B-4), which is an alkali-soluble resin.

(Resin solution (B-5))
In a flask equipped with a cooling tube and a stirrer, 4 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of ethylene glycol monomethyl ether acetate were charged, followed by 15 parts by mass of methacrylic acid and mono succinic acid. 10 parts by mass of (2-methacryloyloxyethyl), 30 parts by mass of N-phenylmaleimide, 25 parts by mass of benzyl methacrylate, 20 parts by mass of styrene and 2.5 parts by mass of α-methylstyrene dimer (chain transfer agent) were charged. After substituting with nitrogen, the reaction solution was heated to 80 ° C. with gentle stirring, and polymerized at this temperature for 3 hours. Then, the temperature of the reaction solution was raised to 100 ° C., 0.5 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the polymerization was continued for 1 hour to obtain a weight average molecular weight. 12,000 acrylic resins were obtained. After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl is prepared so that the non-volatile content is 20% by mass in the previously synthesized resin solution. Ether acetate was added to obtain a resin solution (B-5), which is an alkali-soluble resin.

<Manufacturing of amino group-containing resin>
(Manufacture of Amine Group-Containing Resin (I-1))
39.2 parts of methoxypropyl acetate was charged into a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 110 ° C. while substituting with nitrogen. 11.2 parts of dimethylaminoethyl methacrylate, 47.8 parts of methyl methacrylate, and 1.8 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) were charged into the reaction vessel, and the mixture was stirred until uniform. Then, the reaction was carried out at the same temperature for 3 hours. In this way, a resin-type dispersant solution having an amine value per solid content of 67.8 mgKOH / g and a heavy average molecular weight of 9,000 (Mw) was obtained.
After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and methoxypropyl acetate is added so that the non-volatile content becomes 40% by mass to add an amine group-containing resin. (I-1) was obtained.

<Manufacturing of refined pigments>
(Red refined pigment (R-1))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 (BASF's "IRGAZIN RED 2030") 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , 190 parts of red finely divided pigment (R-1) was obtained.

(Red refined pigment (R-2))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 269 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , 190 parts of red fine pigment (R-2) was obtained.

(Red refined pigment (R-3))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 C.I. I. A red finer pigment (R-3) was obtained in the same procedure as the red finer pigment (R-1) except that it was replaced with Pigment Red 177.

(Yellow refined pigment (Y-1))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 with yellow pigment C.I. I. Pigment Yellow 138 (BASF's "Pariotor Yellow L 0962 HD") was used to obtain a yellow fine pigment (Y-1) in the same procedure as the red fine pigment (R-1).

(Yellow refined pigment (Y-2))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 with yellow pigment C.I. I. Pigment Yellow 150 (“E-4GN” manufactured by LANXESS) was used to obtain a yellow fine pigment (Y-2) in the same procedure as the red fine pigment (R-1).

(Yellow refined pigment (Y-3)
The quinophthalone compound (b) was synthesized according to the synthesis method described in Example 8 of JP2012-226110A to obtain a yellow pigment 1.
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 was obtained. A yellow fine pigment (PY-3) was obtained in the same procedure as the red fine pigment (R-1) except that it was replaced with the obtained yellow pigment 1.

(Green refined pigment (G-1))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 was replaced with a halogenated zinc phthalocyanine green pigment (CI Pigment Green 58). Obtained.

(Green refined pigment (G-2))
To a three-necked flask, add 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (5), 500 parts of N-methylpyrrolidone, and 13.9 parts of diphenyl phosphate, and heat to 90 ° C. The reaction was carried out for 8 hours. This was cooled to room temperature, the product was filtered, washed with methanol, and dried to obtain a green pigment 1 which is a phthalocyanine pigment.
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 was obtained. A green fine pigment (G-2) was obtained in the same procedure as the red fine pigment (R-1) except that it was replaced with the obtained green pigment 1.

(Green refined pigment (G-3))
To a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following chemical formula (5), and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred. The reaction was carried out at 20 ° C. for 6 hours. Then, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added, and the mixture was stirred at 80 ° C. for 1 hour. Then, the mixture was collected by filtration, washed with water, and dried to obtain a pigment in which an average of 10.1 bromine atoms were substituted on the phthalocyanine ring.
Next, to a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment in which an average of 10.1 bromine atoms were substituted on the obtained phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added, and 90 parts were added. It was heated to ° C. and reacted for 8 hours. This was cooled to room temperature, the product was filtered, washed with methanol, and dried to obtain a green pigment 2 which is a phthalocyanine pigment.
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 was obtained in the same procedure as the red fine pigment (R-1) except that the green pigment 2 was replaced with the green fine pigment (G-3).

Chemical formula (5)

(Blue refined pigment (B-1))
To 1000 parts of 98% sulfuric acid, 90 parts of crude copper phthalocyanine synthesized by a known method and 10 parts of the dispersant represented by the chemical formula (6) are added, stirred at 30 ° C. for 2 hours, and then 5000 parts using an aspirator. It was mixed with water to obtain an aqueous solution in which copper phthalocyanine particles were precipitated. The obtained aqueous solution was stirred for 30 minutes, then filtered, washed with water, dried and pulverized to obtain 95 parts of a blue fine pigment (B-1).

Chemical formula (6)

(Blue refined pigment (B-2))
85 parts of crude copper phthalocyanine synthesized by a known method, 15 parts of the dispersant represented by the chemical formula (6), 1000 parts of sodium chloride, and 280 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader manufactured by Inoue Seisakusho and kneaded at 70 ° C. for 8 hours. bottom. After kneading, the mixture was taken out into 20000 parts of an aqueous buffer solution of sodium acetate-sodium acetate (pH 4.0) at 45 ° C., kept warm for 1 hour, and then filtered, washed with water, dried and pulverized to obtain 96 parts of a blue fine pigment (B-2). ..

(Blue refined pigment (B-3))
95 parts of ε-type copper phthalocyanine pigment "LIONOL BLUE E" manufactured by Toyo Color Co., Ltd., 5 parts of dispersant represented by chemical formula (6), 1000 parts of sodium chloride, and 280 parts of diethylene glycol are charged in 1 gallon kneader of stainless steel manufactured by Inoue Seisakusho. , 80 ° C. for 10 hours. After kneading, the mixture was taken out into 20000 parts of an aqueous buffer solution of acetic acid-sodium acetate (pH 4.0) at 30 ° C., and after heat-retaining stirring for 1 hour, 96 parts of blue fine pigment (B-3) was obtained by filtration, washing with water, drying and pulverizing. ..

(Purple refined pigment (V-1))
Dioxazine-based purple pigment C.I. I. Pigment Violet 23 (PV23) (Clariant's "Fast Violet RL") 500 parts, sodium chloride 2500 parts, and polyethylene glycol (Tokyo Kasei Co., Ltd.) 250 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho). It was kneaded at 120 ° C. for 12 hours. Next, this mixture was put into about 5 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, which was then filtered and washed with water to remove sodium chloride and diethylene glycol. It was dried at 80 ° C. for 24 hours to obtain a purple fine pigment (V-1).

(Salt dye compound (AR-1))
With reference to Production Example 50 of Japanese Patent Application No. 2011-261667, C.I. I. A salt-forming dye compound (AR-1) composed of Acid Red 52 and an acrylic resin having a cationic group (quaternary ammonium base) in the side chain was produced.

<Manufacturing of pigment dispersant>
(Pigment Dispersant Solution (K-1))
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of methyl methacrylate, 100 parts of n-butyl acrylate, and 40 parts of propylene glycol monomethyl ether acetate were charged as the first stage synthesis, and nitrogen gas was charged. Replaced with. The inside of the reaction vessel is heated to 80 ° C., 12 parts of 3-mercapto-1,2-propanediol is added, and then 0.2 parts of 2,2'-azobisisobutyronitrile is divided into 20 portions 30 times. It was added every minute and reacted at 80 ° C. for 12 hours, and it was confirmed by solid content measurement that 95% of the reaction was carried out.
Next, as the second stage synthesis, 30 parts of pyromellitic anhydride, 190 parts of propylene glycol monomethyl ether acetate, and 0.40 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added. It was added and reacted at 120 ° C. for 7 hours. It was confirmed by titration that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. In this way, an acidic resin-type pigment dispersant having a poly (meth) acrylate skeleton having an acid value of 42 mgKOH / g per solid content and a weight average molecular weight of 9,800 and a non-volatile content of 40% by mass and having an aromatic carboxyl group. A solution (K-1) was obtained.

<Manufacturing of pigment dispersion>
(Pigment dispersion (PR-1))
After uniformly stirring and mixing 14.0 parts of the red fine pigment (R-1), 15.0 parts of the pigment dispersant solution (K-1), and 71.0 parts of ethylene glycol monomethyl ether acetate (PGMAc). , Using zirconia beads having a diameter of 0.5 mm, disperse with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 3 hours, and then filter with a 5 μm filter to obtain a pigment dispersion of PR254 (PR-1). ) Was obtained.

(Pigment dispersions PR-2 to 5, PY-1 to 3, PG-1 to 3, PB-1 to 3, PV-1, dye solution DV-1)
The pigment dispersions PR-2 to 5, PY-1 to 3, PG- 1-3, PB-1 to 3, PV-1, and dye solution DV-1 were obtained.

The abbreviations in Table 1 are shown below.
-Pigment dispersion solution K-2: EFKA4300 (manufactured by BASF): Basic resin type dispersant (corresponding to amino group-containing resin (I))

<Manufacture of photosensitive coloring composition for color filter>
[Example 1]
(Photosensitive coloring composition (RE-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a colored composition (RE-1).
Pigment dispersion (PR-1): 30.0 parts Pigment dispersion (PR-3): 20.0 parts Resin solution (B-1): 10.0 parts Photopolymerization monomer (C-1): 7 .0 parts Photopolymerization initiator (D-1): 0.6 parts Antioxidant (F-1): 0.4 parts Solvent (E): 32.0 parts methoxypropyl acetate (PGMAC)

[Examples 2 to 76, Comparative Examples 1 to 5]
(Photosensitive coloring composition (RE-2 to RE-81))
RE-2 to RE-81 were obtained in the same manner as in the photosensitive coloring composition (RE-1) except that the compositions and blending amounts shown in Tables 2 to 7 were changed. In this specification, Examples 49 and 50 are reference examples.

<Evaluation of coloring composition for color filter>
The coating film evaluation of the obtained photosensitive coloring composition was carried out by the following method. The results are shown in Tables 2-7.

(Pattern chip evaluation)
The obtained photosensitive coloring composition was applied onto a glass substrate of 100 mm × 100 mm and 0.7 mm so as to have a film thickness of 2.5 μm, and passed through a linear mask having a width of 50 μm and a length of 500 μm at 40 mJ / cm ² . Ultraviolet exposure was performed under the conditions. Then, the potassium hydroxide developer was sprayed by spraying to remove the uncured portion to form a desired pattern. The obtained coating film is heat-treated (post-baked) in an oven at 230 ° C. for 40 minutes, and 10 times the obtained linear patterns are multiplied by 10 with a microscope (“BX-51” manufactured by Olympus Optical Co., Ltd.). When the edge of the line was dented, it was judged to be a chip, and the number of omissions was confirmed. The evaluation was made as follows according to the number of missing pieces. The film thickness of the coating film was measured using Dektak 8 (manufactured by Nippon Vacuum Technology Co., Ltd.).
◎: No pattern chipping 〇: Pattern chipping 1 to 3 △: Pattern chipping 4 to 20 ×: Pattern chipping 21 or more

(Pattern peeling evaluation)
The obtained photosensitive coloring composition was applied onto a glass substrate of 100 mm × 100 mm and 0.7 mm so as to have a film thickness of 2.5 μm, and passed through 75 10 μm × 50 μm rectangular masks under the condition of ^{40 mJ / cm 2.} UV exposure was performed at. Then, the potassium hydroxide developer was sprayed by spraying to remove the uncured portion to form a desired pattern. The obtained coating film was heat-treated (post-baked) in an oven at 230 ° C. for 40 minutes, and pixel peeling was confirmed with a microscope (“BX-51” manufactured by Olympus Optical Co., Ltd.). For the evaluation, the number of peeled pixels out of 75 10 μm × 50 μm rectangular pixels formed on the glass substrate was calculated and evaluated according to the following criteria. The film thickness of the coating film was measured using Dektak 8 (manufactured by Nippon Vacuum Technology Co., Ltd.).
⊚: No pattern peeling / 75 pieces 〇: Pattern peeling 1-5 pieces / 75 pieces △: Pattern peeling 5-10 pieces / 75 pieces ×: Pattern peeling 11 or more / 75 pieces During ~

(Evaluation of contact holes)
The obtained photosensitive coloring composition was applied onto a glass substrate of 100 mm × 100 mm and 0.7 mm so as to have a film thickness of 2.5 μm, and passed through a mask having a pattern having an opening diameter of φ30 μm under the condition of ^{40 mJ / cm 2.} UV exposure was performed at. Then, the potassium hydroxide developer was sprayed by spraying to remove the uncured portion to form a desired pattern. The obtained coating film was heat-treated (post-baked) in an oven at 230 ° C. for 40 minutes, and contact holes of pixels were confirmed with a microscope (“BX-51” manufactured by Olympus Optical Co., Ltd.). The evaluation was made by visually observing the shape of the contact hole and whether or not it was closed, and evaluated according to the following criteria. The film thickness of the coating film was measured using Dektak 8 (manufactured by Nippon Vacuum Technology Co., Ltd.).
⊚: The shape of the contact hole is circular 〇: The shape of the contact hole is elliptical △: The shape of the contact hole is triangular ×: The contact hole is closed

The abbreviations in Tables 2 to 7 are shown below.

<Photopolymerization initiator (D)>
Photopolymerization Initiator D-1:

Photopolymerization Initiator D-2:

Photopolymerization Initiator D-3:

Photopolymerization Initiator D-4:

Photopolymerization Initiator D-5:

Photopolymerization Initiator D-6: 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropan-1-one (BASF's "Irgacure 907")

<Sensitizer>
J-1: 2,4-Diethylthioxanthone ("Kayacure DETX-S" manufactured by Nippon Kayaku Co., Ltd.)
J-2: 4,4'-bis (diethylamino) benzophenone ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)

<Photopolymerizable monomer (C)>
C-1: Dipentaerythritol hexaacrylate ("Aronix M-402" manufactured by Toagosei Co., Ltd.)
C-2: Trimethylolpropane triacrylate ("Aronix M-309" manufactured by Toagosei Co., Ltd.)
C-3: Trimethylolpropane EO-modified triacrylate ("Aronix M-350" manufactured by Toagosei Co., Ltd.)
C-4: Trimethylolpropane PO-modified triacrylate ("Aronix M-310" manufactured by Toagosei Co., Ltd.)
C-5: Pentaerythritol tetraacrylate ("Aronix M-450" manufactured by Toagosei Co., Ltd.)
C-6: Ethoxylated isocyanuric acid triacrylate ("A-9300" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
C-7: Dipentaerythritol pentaacrylate hexamethylene diisocyanate (reaction product of dipentaerythritol pentaacrylate and hexamethylene diisocyanate)
C-8: Pentaerythritol triacrylate hexamethylene diisocyanate C-9: Polyfunctional urethane acrylate (KSM "KUA-4I")

<Antioxidant (F)>
(Phenolic antioxidant)
F-1: 2 pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (BASF's "IRGANOX 1010")
F-2: Thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (BASF's "IRGANOX 1035")
F-3: Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (BASF's "IRGANOX 1076")
F-4: Benzen propanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester (BASF "IRGANOX 1135")

(Phosphoric acid-based antioxidant)
F-5: Tris phosphite (2,4-di-tert-butylphenyl) (BASF's "IRGAFOS 168")
F-6: Acrylic acid 1'-hydroxy [2,2'-ethylidenebis [4,6-bis (1,1-dimethylpropyl) benzene]] -1-yl (Sumitomo Chemical Co., Ltd. "SUMIKIZER (R) GS" ”)
F-7: Acrylic acid 1'-hydroxy [2,2'-methylenebis (4-methyl-6-tert-butylbenzene)]-1-yl ("SUMILLIZER (R) GM" manufactured by Sumitomo Chemical Co., Ltd.)
F-8: Bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] (2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diyl) Bis (2,2-dimethyl-2,1-ethanediyl) ("SUMILLIZER (R) GA-80" manufactured by Sumitomo Chemical Co., Ltd.)

(Sulfur-based antioxidant)
F-9: Bis [3- (dodecylthio) propionic acid] 2,2-bis [[3- (dodecylthio) -1-oxopropyloxy] methyl] -1,3-propanediyl (Sumitomo Chemical Co., Ltd. "SUMILLIZER (" SUMILIZER (Sumitomo Chemical Co., Ltd.) R) TP-D ")

<Polymerization inhibitor (G)>
G-1: Methyl hydroquinone (“MH” manufactured by Seiko Kagaku Co., Ltd.)

<Phosphate ester compound (H) having an ethylenically unsaturated group>
H-1: (corresponding to the general formula (1)): Ethylene oxide-modified dimethacrylate phosphate ("PM-21" manufactured by Nippon Kayaku Co., Ltd.)
H-2: 2-Acryloyloxyethyl acid phosphate ("Light Acrylate P-1A (N)" manufactured by Kyoeisha Chemical Co., Ltd.)
H-3: 2-Dimethacloyloxyethyl phosphate ("P-2M" manufactured by Kyoeisha Chemical Co., Ltd.)
H-4: (corresponding to the general formula (1)): Ethylene oxide-modified diphenyl methacrylate phosphate

<Amino group-containing resin (I)>
I-2: BYK-21116 (manufactured by Big Chemie Japan)
I-3: BYK-6919 (manufactured by Big Chemie Japan)

・ Organic solvent: PGMAC

It is composed of at least one selected from the group consisting of the antioxidant (F) and the polymerization inhibitor (G) of the present invention, a phosphoric acid ester compound (H) having an ethylenically unsaturated group, and an amino group-containing resin (I). A photosensitive coloring composition for a color filter containing at least one selected from the group, wherein the content of the colorant (A) is 25% by mass to 45% by mass with respect to the total solid content of the photosensitive coloring composition for a color filter. A photosensitive coloring composition for a color filter, which is by mass% and has a content of the photopolymerized monomer (C) of 30% by mass to 55% by mass with respect to the total amount of solids in the photosensitive coloring composition for a color filter. By using the above, a circular contact hole could be formed without pattern chipping and pattern peeling, and the resolution was excellent.

On the other hand, when it does not contain at least one selected from the group consisting of the antioxidant (F) and the polymerization inhibitor (G), the phosphoric acid ester compound (H) having an ethylenically unsaturated group and the amino group-containing resin (I). ) Is not contained, or the content of the photopolymerized monomer (C) is 30% by mass to 55% by mass with respect to the total amount of solids in the photosensitive coloring composition for a color filter. The coloring composition is out of the range of%, or when the content of the colorant (A) is out of the range of 25% by mass to 45% by mass with respect to the total solid content in the photosensitive coloring composition for a color filter. , Pattern chipping and pattern peeling were often seen, and the shape of the contact hole was also distorted or blocked.

Therefore, it was possible to form a circular contact hole without pattern chipping and pattern peeling, and it was possible to produce a coloring composition having excellent resolution.

Further, when the same evaluation was performed on the color filter produced by using the above-mentioned coloring composition, suitable results were obtained in pattern chipping and pattern peeling, and production with high yield could be performed. As a result, it can be suitably used in a liquid crystal display device, a solid-state image sensor, and an organic EL display device using the above color filter.

Claims (6)

Photosensitive coloring for color filters containing a colorant (A), a resin (B) ( excluding the resin (I)), a photopolymerizable monomer (C), a photopolymerization initiator (D) and a solvent (E). It ’s a composition,
Further, a phosphoric acid ester compound (H) having at least one selected from the group consisting of an antioxidant (F) and a polymerization inhibitor (G) and an ethylenically unsaturated group represented by the following general formula (1). And at least one selected from the group consisting of the amino group-containing resin (I).
General formula (1)
[CH ₂ = CR ^1- CO-O-X ^1- O-CO-X ^2- O] _n- PO- (OR ² ) _m
In (formula (1), R ¹ and R ² are each independently hydrogen atom, and .X ¹ represents an aryl group which may have an alkyl group or a substituted group which may have a substituent X ² represents an alkylene group which may independently have a substituent. M is an integer of 0 to 2, and n is an integer of 1 to 3).
The content of the phosphoric acid ester compound (H) having an ethylenically unsaturated group is 0.5% by mass or more and 5.0% by mass or less with respect to the total solid content in the photosensitive coloring composition for a color filter.
The content of the colorant (A) is 25% by mass or more and 45% by mass or less with respect to the total solid content of the photosensitive coloring composition for a color filter, and the content of the photopolymerizable monomer (C) is A photosensitive coloring composition for a color filter, which is 30% by mass or more and 55% by mass or less based on the total solid content of the photosensitive coloring composition for a color filter. A claim that the total content of the antioxidant (F) and the polymerization inhibitor (G) is 0.1% by mass or more and 5.0% by mass or less with respect to the total solid content of the photosensitive coloring composition for a color filter. Item 2. The photosensitive coloring composition for a color filter according to Item 1. The content of amino group-containing resin (I) is not less than 0.1 mass% 5.0 mass% or less with respect to the total solid content of the color filter for the photosensitive coloring composition according to claim 1 or 2 Photosensitive coloring composition for color filters. The photosensitive coloring for a color filter according to any one of claims 1 to 3, which comprises an antioxidant (F) and a phosphoric acid ester compound (H) having an ethylenically unsaturated group represented by the general formula (1). Composition. The photosensitive coloring composition for a color filter according to any one of claims 1 to 4 , wherein the antioxidant (F) is a phenolic antioxidant. A color filter comprising a filter segment formed from the photosensitive coloring composition for a color filter according to any one of claims 1 to 5 on a substrate.