JP2019090920A - Photosensitive coloring composition for color filter and color filter - Google Patents

Abstract

To provide a photosensitive coloring composition for a color filter which has no pattern chipping and separation and is excellent in linearity and adhesion, and has good development margin.SOLUTION: A photosensitive coloring composition for a color filter contains a colorant (A), a resin (B) (excluding resin (I)), a photopolymerizable monomer (C), a photopolymerization initiator (D) and a solvent (E), and further contains at least one selected from the group consisting of an antioxidant (F) and a polymerization inhibitor (G) and at least one selected from the group consisting of a phosphoric ester compound (H) having an ethylenically unsaturated group and an amino group-containing resin (I), in which a content of the colorant (A) is 25 mass% to 45 mass% with respect to the total content of a solid content of the photosensitive coloring composition for a color filter, and a content of the photopolymerizable monomer (C) is 30 mass% to 55 mass% with respect to the total content of a solid content of the photosensitive coloring composition for a color filter.SELECTED DRAWING: None

Description

A liquid crystal display panel with a high transmittance structure has been developed which employs a color filter on array (COA) substrate in which color filters are formed on an array substrate. In the COA method, the aperture ratio can be greatly increased, and high image quality and low power consumption of the color liquid crystal display device can be achieved. However, since it is necessary to provide a contact hole for connecting the transparent electrode and the TFT to the pixel of the COA type, the photosensitive coloring composition for a color filter for forming the pixel needs to have better resolution.
A method (see Patent Document 1) using a specific initiator for improving resolution, 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 been increased as a required quality item, and it has become necessary to increase the colorant content in the resist, but when the content of the colorant is increased, the irradiation light at the time of exposure However, curing of pixel boundaries (edges of the formed pattern) of the photosensitive coloring composition for color filters is insufficient, and pattern nicks in which some pixels are chipped easily occur. Therefore, if the amount of photopolymerization initiator is increased in order to cure to the pixel boundary of the photosensitive coloring composition for color filter, the contact hole is closed and the transparent electrode and the TFT can not be connected, and the COA color liquid crystal display device can not be manufactured. . Further, since the resolution of the contact hole is lowered by the increase of the coloring agent having no developability, it is necessary to increase the amount of the photopolymerizable monomer, but when the equivalent amount of double bond is increased, a large curing shrinkage occurs upon irradiation with glass Because the adhesion to the film is reduced, pattern peeling is likely to occur, but the COA system is therefore required to produce a high resolution pattern without causing pattern peeling or pattern breakage as compared with a normal color filter.

JP 2001-324611 A JP 2000-214580 A

  The present invention particularly uses a photosensitive coloring composition for color filters with excellent adhesion that does not cause pattern peeling or pattern peeling, while excellent high resolution such as the COA system is required, and the same. To provide a color filter.

As a result of extensive research to solve the above problems, the present inventors
Photosensitivity for color filter containing coloring agent (A), resin (B) (except resin (I)), photopolymerizable monomer (C), photopolymerization initiator (D) and solvent (E) A coloring composition,
Furthermore, at least one selected from the group consisting of an antioxidant (F) and a polymerization inhibitor (G),
At least one selected from the group consisting of phosphoric acid ester compounds (H) having an ethylenically unsaturated group and amino group-containing resin (I) 25% by mass to 45% by mass with respect to the total solid content of the coloring composition,
The photosensitive coloring composition for color filters whose content of a photopolymerizable monomer (C) is 30 mass%-55 mass% with respect to solid content whole quantity of the photosensitive coloring composition for color filters,
Even with a large amount of photosensitive colorants, the photopolymerizable monomer and the colorant can suppress thickening of the pixels, and the photopolymerizable initiator can be applied to the entire photosensitive colorant without blocking the contact holes of the pixels that are important in the COA method. Since it is possible to increase the amount, curing proceeds to the boundary of the pixel, and the adhesion with the substrate is improved by adding a phosphoric acid ester compound having an ethylenically unsaturated group and an amino group-containing resin, and the photopolymerization single It has been found that it is possible to provide a photosensitive coloring composition for color filters and a color filter using the same, since it is possible to increase the amount of mer, so that it has excellent high resolution and excellent adhesion without causing pattern peeling or pattern peeling. The present invention has been made based on the findings.

<1> Color filter containing coloring agent (A), resin (B) (however, except resin (I)), photopolymerizable monomer (C), photopolymerization initiator (D) and solvent (E) Photosensitive coloring composition for use in
Furthermore, it comprises at least one member 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 to 45% by mass with respect to the total solid content of the photosensitive coloring composition for color filters, and is photopolymerizable The photosensitive coloring composition for color filters whose content of a monomer (C) is 30 to 55 mass% with respect to solid content whole quantity of the photosensitive coloring composition for color filters.

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

Content of the phosphoric acid ester compound (H) which has a <3> ethylenic unsaturated group is 0.1 mass% or more and 5.0 mass% or less with respect to solid content whole quantity in the photosensitive coloring composition for color filters Or
Photosensitive coloring composition for color filter as described above, wherein the content of the amino group-containing resin (I) is 0.1% by mass or more and 5.0% by mass or less based on the total amount of solid content of the photosensitive coloring composition for color filter object.

The photosensitive coloring composition for said color filters containing <4> antioxidant (F) and the phosphoric acid ester compound (H) which has an ethylenically unsaturated group.

The photosensitive coloring composition for said color filters whose <5> antioxidant (F) is a phenolic antioxidant.

The photosensitive coloring composition for said color filters whose phosphoric acid ester compound (H) which has a <6> ethylenic unsaturated group is a phosphoric acid ester compound represented by following General formula (1).
General formula (1)
[CH = CR ¹ -CO-O-X ¹ -O-CO-X ² -O] _n -PO- (OR ² ) _m
(In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. X ¹ and Each X ² independently represents an alkylene group which may have a substituent, m represents an integer of 0 to 2, and n represents an integer of 1 to ^3. )

The color filter which comprises the filter segment formed from the said photosensitive coloring composition for color filters on a <7> board | substrate.

  The photosensitive coloring composition for color filters of the present invention is required to have high adhesion such as pattern peeling or pattern peeling while being required to have excellent high resolution like the COA system. A composition and a color filter using the same can be provided.

The photosensitive coloring composition for color filters of the present invention comprises a colorant (A), a resin (B) (except for the resin (I)), a photopolymerizable monomer (C) and a photopolymerization initiator (D). And a solvent (E), which is a photosensitive coloring composition for color filters,
Furthermore, it comprises at least one member 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) And at least one selected from the group consisting of
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 color filters, and the content of the photopolymerizable monomer (C) is It is characterized by being 30 mass% or more and 55 mass% or less with respect to solid content whole quantity of the photosensitive coloring composition for color filters.

Hereinafter, the present invention will be described in detail.
In the present application, when it is described as “(meth) acryloyl”, “(meth) acrylic”, “(meth) acrylic acid” or “(meth) acrylate”, unless otherwise described, Acryloyl and / or methacryloyl ”,“ acrylic and / or methacrylic ”,“ acrylic acid and / or methacrylic acid ”or“ acrylate and / or methacrylate ”. In addition, “CI” listed in the present specification means a color index (CI).

<Colorant (A)>
The photosensitive coloring composition for color filters of the present invention contains a colorant (A). Content of a coloring agent (A) is 25 mass%-45 mass% with respect to solid content whole quantity of the photosensitive coloring composition for color filters. By setting this range, sufficient color reproducibility can be obtained, and it is preferably 30% by mass or more, more preferably 35% by mass or more.
As a coloring agent, an organic or inorganic pigment can be used individually or in mixture of 2 or more types. Among the pigments, pigments having high color developability and high heat resistance are preferable, and usually organic pigments are used. Below, the specific example of the organic pigment which can be used for the photosensitive coloring composition of this invention is shown by a color index number. Moreover, as a coloring agent, dye can be contained in the range which does not reduce heat resistance.

  Examples of red pigments 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: 81, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 181, 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, 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 dyes, anthraquinone dyes, quinophthalone dyes, isoindoline dyes, perinone dyes, perylene dyes and benzimidazolone dyes are exemplified from the viewpoint of lightness and coloring power. Specifically, C.I. I. Pigment red 176, 177, 179, 254, 242, and a naphthol azo pigment represented by the following general formula (2) are preferable.

General formula (2)

[In 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 each independently represent 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 , -NHCOR ¹² or SO ₂ NHR ¹³ is represented. R ⁷ to R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

  Examples of blue pigments 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. Among these, from the viewpoint of lightness and coloring power, C.I. I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment blue 15: 6. Moreover, the aluminum phthalocyanine pigment etc. which are described in Unexamined-Japanese-Patent No. 2004-333817, patent 4893859 grade | etc., Can also be used, It does not specifically limit to these.

  As a green pigment, for example, 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. It can be mentioned. Among these, from the viewpoint of lightness and coloring power, C.I. I. Pigment green 7, 36, 58, 59, 62, 63. Moreover, the zinc phthalocyanine pigment etc. which are described in Unexamined-Japanese-Patent No. 2008-19383, Unexamined-Japanese-Patent No. 2007-320986, Unexamined-Japanese-Patent No. 2004-70342 etc. can also be used, It does not specifically limit to these.

Examples of yellow pigments 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, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 , 174, 175, 176, 180, 181, 182, 183, 185, 188, 189, 190, 191, 191, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 203, 204, 205, 206, 207, 208, 231, and the quinophthalone compound etc. which are described in Unexamined-Japanese-Patent No. 2012-226110 etc. can be mentioned. Among these, from the viewpoint of lightness and coloring power, C.I. I. Pigment yellow 138, 139, 150, 185, 231, and a quinophthalone compound described in JP 2012-226110.
Although the quinophthalone compound (a)-(r) etc. which are shown below are mentioned as a specific example of a quinophthalone compound, this invention is not limited to these.

  Examples of purple pigments 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, 25, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned. Among these, from the viewpoint of lightness and coloring power, C.I. I. Pigment violet 19 or 23, and more preferably C.I. I. Pigment violet 23.

  As an orange pigment, for example, C.I. I. Pigment orange 38, 43, 64, 71 or 73, etc. are raised. Among them, from the viewpoint of lightness and coloring power, C.I. I. Pigment oranges 38, 43 and 64 are preferred.

  Examples of the black photosensitive coloring composition for forming a black matrix include carbon black, aniline black, anthraquinone black pigments, perylene black pigments, specifically C.I. I. Pigment blacks 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 a black pigment, carbon black is preferable in terms of price and light-shielding size, and carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, a blue pigment and a purple pigment can be used together to a black photosensitive coloring composition.

  Further, as inorganic pigments, barium sulfate, zinc flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black And metal oxide powders such as synthetic iron black, titanium oxide and iron tetraoxide, metal sulfide powders, metal powders and the like. The inorganic pigment is used in combination with an organic pigment in order to ensure good coatability, sensitivity, developability, etc. while maintaining a balance between chroma and lightness.

  The coloring composition of the present invention can also use a dye as a coloring agent. As the dye, any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, architectural dyes, sulfur dyes and the like can be used. In addition, these may be in the form of derivatives or laked lakes of dyes.

  The chemical structure of the dye includes, for example, azo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthraquinone dyes, Pyridone dyes, carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes Dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes Indigo dyes, mention may be made thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and a dye structure derived from a dye selected from those metal complex dyes.

  Among these dye structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium, from the viewpoint of color characteristics such as hue, color separation, and color unevenness. Dye structures derived 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, phthalocyanine dyes More preferred is a dye structure derived from a dye selected from the dye series. Specific dye compounds that can form a dye structure are described in “New Dye Handbook” (Organic Synthetic Chemistry Association, edited by Maruzen, 1970), “The Society of Dyers and colourists”, “Dye Handbook” (Ogawara et al. Ed., Kodansha, 1986).

<Resin (B)>
The coloring composition for color filters of the present invention contains a resin (B).
The resin (B) is for dispersing or permeating a pigment, and examples thereof include thermoplastic resins. 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 range of 400 to 700 nm in the visible light range. 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 acidic substituent-containing ethylenically unsaturated monomer. Furthermore, in order to further improve the photosensitivity, an active energy ray curable resin having an ethylenically unsaturated double bond can also be used.

  As a thermoplastic resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin And polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  As a vinyl type alkali-soluble resin which copolymerized the acidic substituent containing ethylenic unsaturated monomer, resin which has acidic substituents, such as a carboxyl group and a sulfone group, is mentioned, for example. Specifically as the alkali-soluble resin, an acrylic resin having an acidic substituent, an α-olefin / (maleic anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, Or isobutylene / (anhydride) maleic acid copolymer and the like. Among them, at least one resin selected from an acrylic resin having an acidic substituent and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, is preferably used because it is high in heat resistance and transparency. Be

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

[Method (i)]
As the method (i), for example, to a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers. A carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added, and a polybasic acid anhydride is further reacted with the produced hydroxyl group 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, 3,4-epoxybutyl (meth) acrylate And 3,4-epoxycyclohexyl (meth) acrylates, which may be used alone or in combination of two or more. Glycidyl (meth) acrylate is preferred from the viewpoint of the reactivity with the unsaturated monobasic acid in the next step.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano-substituted, etc. Monocarboxylic acids and the like can be mentioned, and these may be used alone or in combination of two or more.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, which may be used alone or in combination of two or more. I do not mind. The remaining anhydride is obtained by using tricarboxylic acid anhydride such as trimellitic acid anhydride or using tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride, if necessary, such as increasing the number of carboxyl groups. It is also possible to hydrolyze the group, etc. In addition, when tetrahydrophthalic anhydride having an ethylenically unsaturated double bond, or maleic anhydride is used as a polybasic acid anhydride, the number of ethylenically unsaturated double bonds can be further increased.

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

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

  As the ethylenically unsaturated monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol There may be mentioned hydroxyalkyl methacrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, which may be used alone or in combination of two or more. In addition, polyether mono (meth) acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and / or butylene oxide etc. to the above hydroxyalkyl (meth) acrylate, poly γ-valerolactone, poly ε-caprolactone, and / or Polyester mono (meth) acrylates 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 coating foreign matter suppression.

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

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

  In addition, from the viewpoints of pigment dispersibility, stability, developability, and heat resistance, a carboxyl group that functions as a pigment adsorption group and an alkali-soluble group during development, an aliphatic group that functions as an affinity group for a pigment carrier and a solvent, and a fragrance The balance of group groups is important for the dispersibility of the pigment, the developer permeability in the coating film, the developer solubility of the uncured portion, and the durability, and a resin with an acid value of 20 to 300 mg KOH / g should be used preferable. If the acid value is less than 20 mg KOH / g, the solubility in a developer is poor, and it is difficult to form a fine pattern. When it exceeds 300 mg KOH / g, fine patterns may not be left.

  The resin (B) is preferably used in an amount of 30 parts by mass or more based on 100 parts by mass of the total weight of the colorant (A) because the film formability and various resistances are good, and the pigment concentration is high, It is preferable to use in an amount of 500 parts by mass or less, because good color characteristics can be exhibited. More preferably 100 to 400 parts by mass. More preferably, it is 160-320 mass parts. The chromaticity range can be expanded by the composition ratio of such a pigment.

<Photopolymerizable monomer (C)>
The photosensitive coloring composition for color filters of the present invention contains a photopolymerizable monomer (C).
The photopolymerizable monomer includes a monomer or an oligomer which is cured by ultraviolet light or heat to form a transparent resin. Content of a photopolymerizable monomer (C) is 30 mass%-55 mass% with respect to the total solid amount of the photosensitive coloring composition for color filters. By setting it as this range, it can be set as the composition which has high resolution and pattern chipping and is excellent in adhesiveness. When the amount is less than 30% by mass, the resolution is poor. When the amount is more than 55% by mass, chipping and peeling of the pattern occur. Preferably it is 30 to 45%, more preferably 35 to 40%.

Examples of monomers and oligomers that cure by ultraviolet light and heat to form a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 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, trimethylolpropane tri (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, trimethylol Lopan PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, isocyanuric acid EO modified di (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, penta Erythritol 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, tricyclodecanyl (meth) acrolein , Ester acrylates, (meth) acrylic esters of methylolated melamine, epoxy (meth) acrylates, urethane acrylates and other various acrylic esters and methacrylic esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, Ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinyl formamide, acrylonitrile and the like can be mentioned, but it is not necessarily limited thereto.
These photopolymerizable compounds can be used alone or in combination of two or more at an arbitrary ratio as needed.

  As these commercial products, KAYARAD R-128H, KAYARAD R526, KAYARAD PEG400DA, KAYARAD MAND, KAYARD NPGDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, KAYARAD R 712, KAYARAD R 712, KAYARAD R 712 manufactured by Nippon Kayaku Co., Ltd. -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, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and Toa Go -Made M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400 , M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, biscoat # 310 HP manufactured by Osaka Organic Co., Ltd. Biscoat # 335 HP, Viscote # 700, Viscote # 295, Viscote # 330, Viscote # 360, Viscote # GPT, Viscote # 400, Viscote # 405, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd. can be suitably used. .

(Photopolymerizable monomer having an acid group)
The photopolymerizable monomer in the present invention may contain a photopolymerizable monomer having an acid group. As an acid group, a sulfonic acid group, a carboxyl group, a phosphoric acid group etc. can be mentioned.

  As the photopolymerizable monomer having an acid group, for example, an esterified product of free hydroxyl group-containing poly (meth) acrylates of polyhydric alcohol and (meth) acrylic acid, and dicarboxylic acids; polyhydric carboxylic acid, Examples thereof include esterified products with monohydroxyalkyl (meth) acrylates. As a specific example, monohydroxy oligo acrylates or mono hydroxy oligo methacrylates such as trimethylol propane diacrylate, trimethylol propane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc. And free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic 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 free carboxyl group-containing oligoesters with monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. However, the effects of the present invention are not limited to these.

  As these commercial products, Biscoat # 2500P made by Osaka Organic Co., Ltd., and M-5300, M-5400, M-5700, M-510, M-520 etc. made by Toa Synthetic Co., Ltd. can be suitably used.

  These photopolymerizable monomers having an acid group can be used alone or in combination of two or more at an arbitrary ratio as needed.

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

  As the (meth) acrylate having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri ( 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 Methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloyl propyl methacrylate, epoxy group containing The reaction product of compound and the carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

  Moreover, as polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate etc. are mentioned.

  In addition, although the structure of alcohol is not limited, it is preferable to use a polyhydric alcohol because the degree of crosslinking of the cured coating film is increased and the coating film resistance is increased. Examples of polyhydric alcohols include propylene glycol, ethylene glycol, glycerin, trimethylolpropane and pentaerythritol.

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

  These photopolymerizable monomers having a urethane bond can be used alone or in combination of two or more at an arbitrary ratio as needed.

<Photoinitiator (D)>
In the photosensitive composition of the present invention, a photopolymerization initiator is added to cure the composition by ultraviolet irradiation and form a filter segment by a photolithography method, and a solvent development type or alkali development type photosensitive composition is added. It can be prepared in the form of

  As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-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) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, or 3,3 ', Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, or 2,4-diethyl thioxanthone Etc .; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-metho) Ciphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyl] Oxime)], or oxime ester compounds such as ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); Phosphine compounds such as 2,4,6-trimethylbenzoyl) phenyl phosphine oxide or 2,4,6-trimethylbenzoyl diphenyl phosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone and the like Borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.

These photopolymerization initiators can be used alone or in combination of two or more at an arbitrary ratio as required.
As a commercial product, as an acetophenone type compound, "IRGACURE 907" (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one), all manufactured by BASF, "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) -butan-1-one, all as phosphine compounds, “IRGACURE 819” (bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide) manufactured by BASF, "IRGACURE TPO" (2,4,6-trimethyl benzoyl diphenyl phos In'okisaido), and the like.

  Among these, in the present invention, it is preferable to contain an oxime ester compound.

(Oxime ester compounds)
The oxime ester compound causes the cleavage of the N-O bond of the oxime by absorbing ultraviolet light to generate an iminyl radical and an alkyloxy radical. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small exposure amount. When the coloring agent concentration of the photosensitive coloring composition for color filters is high, the ultraviolet light transmittance of the coating film may be low and the curing degree of the coating film may be low. However, oxime ester compounds are preferable because they have high quantum efficiency. Used for More preferably, they are oxime ester type photoinitiators represented by the general formula (3) or (4).

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

In General Formula (3), Y ¹ and Y ² are each independently a hydrogen atom or an alkyl group or an aryl group which may have a substituent, and Y ⁴ and Y ⁶ are each independently Is a hydrogen atom or an alkyl or aryl group which may have a substituent, Y ⁵ is a hydrogen atom or an alkyl or aryl group which may have a substituent, or Y 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 linear, branched and cyclic alkyl groups. Specifically, methyl group, ethyl group, normal propyl group, isopropyl group, n-butyl group, t -Butyl, n-hexyl, cyclohexyl, n-octyl, hexadecyl and the like.
As an aryl group in General formula (3), a phenyl group, a naphthyl group, anthryl group etc. are mentioned.
The heterocyclic group in the general formula (3) includes a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a pyrrol ring, a furan ring, a thiophene ring, an imidazole ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazol ring, an isoxazole Derived by removing a hydrogen atom from a heterocycle such as a ring, isothiazole ring, triazole ring, thiadiazole ring, oxadiazole ring, quinoline ring, benzofuran ring, indole ring, morpholine ring, pyrrolidine ring, piperidine ring, tetrahydrofuran ring A monovalent group is mentioned.

Examples of the substituent which may be possessed include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group, p-tolyloxy group and the like An alkoxycarbonyl group such as an aryloxy group, a methoxycarbonyl group, a butoxycarbonyl group and a phenoxy carbonyl group, an acetoxy group, an acyloxy group such as a propionyloxy group and a benzoyloxy group, an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group and a methacryloyl group Group, an acyl group such as methoxalyl group, an alkylsulfanyl group such as methylsulfanyl group and tert-butylsulfanyl group, an arylsulfanyl group such as phenylsulfanyl group and p-tolylsulfanyl group, methylamino group, cyclohexyl Alkylamino group such as mino 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 Alkyl group such as dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, In addition to aryl groups such as anthryl group and phenanthryl group, and heterocyclic groups such as furyl group and thienyl group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group , Nitro group, cyano group, trifluoromethyl group Trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, trimethyl ammonium Niu mill group, dimethylsulfoxide Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like.
In addition, one or more of these substituents may be present, or one or more may be present, and further, the hydrogen atom of these substituents may be further substituted by another substituent.

Y ¹ is preferably an aryl group which may have a substituent, Y ² is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, and Y ⁴ and Y ⁶ are as Preferably it is a hydrogen atom, and preferably Y ⁵ is a hydrogen atom or a Y ⁷ -CO- group.

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

[Oxime ester 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 each independently represent a hydrogen atom or an alkyl or aryl group which may have a substituent, and Y ^{7 to} Y ¹⁴ each independently represent a hydrogen atom or a substituent An alkyl group, an aryl group, a nitro group, or a Y ¹⁵ -CO- group which may have a group, and Y ¹⁵ is a hydrogen atom or an alkyl group or an aryl group which may have a substituent It is.

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

  The substituent which may be possessed is synonymous with the substituent in 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 having 1 to 20 carbon atoms which may have a substituent or a substituent And Y ^{7 to} Y ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl which may have a substituent. Group, a nitro group or a Y ¹⁵ -CO- group, and among them, a hydrogen atom is preferable as Y ^{7 to} Y ⁹ , Y ^{10 to} Y ¹² and Y ¹³ , and a nitro group or Y ¹⁵ is preferable as Y ^11. It is a -CO- group, more preferably a Y ¹⁵ -CO- group, and Y ¹⁵ is preferably an aryl group which may have a substituent.

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

"Oxime ester photopolymerization initiator represented by 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 in the general formula (4) Y ^{7 to} Y ¹⁰ and Y ^{12 to} Y ¹³ are hydrogen atoms.
^Further, it is preferable that ^{Y 11} is ^Y 15 -CO- group, or a nitro group. Y ¹⁵ is the same as the substituent 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 which may have a substituent, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group or a methoxaryl group. More preferably, it is a benzoyl group which may have a substituent or a nitro group. The Y ^14, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an aryl group which may have a substituent is preferable.

Moreover, as a substituent in the benzoyl group which may have a substituent, a C1-C20 alkyl group or an alkyloxy group is preferable. Furthermore, as the alkyl group, a methyl group or an ethyl group is preferable, and among the alkyloxy groups, a linear, branched chain having 2 to 18 carbon atoms and optionally interrupted by one or more -O- A monocyclic or fused polycyclic alkyloxy group is preferable, and it is a linear, branched, monocyclic or fused polycyclic ring having 2 to 18 carbon atoms in Y ¹ and optionally interrupted by one or more -O- It is synonymous with the alkyloxy group.

Y ² is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, and preferred examples of the substituent include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl It is a cycloalkyl group such as cyclooctadecyl group. Further, an aryl group which may have a substituent is preferable, and as the substituent, 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. Alkoxy groups such as are preferred.

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

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

General formula (4b)

The general formula (4) corresponds to the case where Z in the general formula (4) is a -CO- group, and Y ³ is a monovalent organic group containing a carbazole group which may have a substituent; And an oxime ester-based photopolymerization initiator.
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 preferable that it is a good aryl group.
The substituent of the aryl group which may have a substituent is preferably an acyl group such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group or methoxalyl group, and more preferably benzoyl group.

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

  As commercially available products of these oxime ester compounds, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IRGACURE OXE-01), ethanone from BASF. 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02), N-1919 (manufactured by ADEKA Corporation), There are commercially available TRONLY TR-PBG-304, TRONLY TR-PBG-305, and TRONLY TR-PBG-309 (all of which are manufactured by Changshu Strong New Materials Co., Ltd.). Furthermore, in addition to this, the oximes described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. It is also possible to use an ester photoinitiator.

  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 the amount is less than 2 parts by mass, the adhesion of the formed pattern to the substrate may be poor. If the amount is more than 50 parts by mass, problems with developability may occur or lightness may decrease after heat treatment at 230 ° C.

<Sensitizer>
Furthermore, the photosensitive composition of the present invention can contain a sensitizer.
As sensitizers, unsaturated ketones represented by chalcone derivatives, dibenzalacetone etc., 1,2-diketone derivatives represented by benzyl and camphorquinone etc., benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapyrazino porphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo porphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrilium derivative, tetraphyrin derivative, anurene derivative, spiropyran derivative, spirooxazine Derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acyl phosphine oxide, methylphenyl glyoxylate, benzyl, 9, 10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone , 4,4'-bis (diethylamino) benzophenone and the like.

Among the above-mentioned sensitizers, sensitizers which can be particularly preferably sensitized include thioxanthone derivatives, Michler's ketone derivatives and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 1-chloro-4-propoxy thioxanthone, 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 combination of two or more at an arbitrary ratio as needed.

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

  More specifically, edited by Ogawara Shin et al., "Dye Handbook" (1986, Kodansha), edited by Ogawara Shin et al., "Chemicals of functional dyes" (1981, CMC), edited by Ikemori Tadajiro et al. Specific examples thereof include, but are not limited to, the sensitizers described in “Specially functional materials” (1986, CMC). In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be contained.

  The content when using the sensitizer is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the radical photopolymerization initiator contained in the coloring composition, and 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 benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds. .

  The content of the ultraviolet absorber is preferably 5 to 70% by mass in 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When the content of the ultraviolet absorber is less than the above, the effect of the ultraviolet absorber is small and the resolution can not be ensured, and when the content is more than the above, the sensitivity is low and the pixel peeling and the hole diameter are larger than the design values May cause problems such as

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

  The total content of the photopolymerization initiator and the ultraviolet light absorber is preferably 1 to 20% by mass in 100% by mass of the solid content of the photosensitive coloring composition for color filter. When the total content of the photopolymerization initiator and the ultraviolet light absorber is less than the above, the adhesion is weakened to cause peeling of the pixel. When the total content 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 color filter contains a sensitizer, the content of the photopolymerization initiator is determined to include the content of the sensitizer.

  2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, octyl-3 [3-tert-butyl as a benzotriazole type organic compound -4-Hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H -Benzotriazol-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- Compounds of benzotriazol-2-yl)-(1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl esters, 2- (2H-benzotriazol-2-yl) -4,6 -Bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3 -Tetramethylbutyl) phenol is mentioned.

  More specifically, BASF "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

  Examples of triazine organic compounds include 2- [4,6-di (2,4-xylyl) -1,3,5-triazin-2-yl] -5-octyloxyphenol and 2- [4,6-bis (2,4-Dimethylphenyl) -1,3,5-triazin-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-glycidic ester, 2,4-bis "2-hydroxy-4-butoxyphenyl" -6- (2,4-dibutoxyphenyl) -1,3-5-triazine and the like.

  More specifically, "KEMISORB 102" manufactured by Chemi-Pro Chemical, "TINUVIN 400" manufactured by BASF, "TINUVIN 405", "TINUVIN 460", "TINUVIN 477-DW", "TINUVIN 479", "TINUVIN 1577", "ADEKA STAB LA-46" and "ADEKA STAB LA-F70" by ADEKA, "CYASORB UV-1164" by Sun Chemical Co., etc. are mentioned.

  Examples of benzophenone organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n- Examples include octoxybenzophenone, 2,2-dihydroxy-4-methoxybenzophenone and the like.

  More specifically, “KEMISORB 10”, “KEMISORB 11”, “KEMISORB 11S”, “KEMISORB 12”, “KEMISORB 111” manufactured by Chemi-Pro Chemical, “SEESORB 101”, “SEESORB 107” manufactured by Shipro Chemicals, Company-made "Adeka stub 1413" etc. is mentioned.

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

  In addition, polyfunctional aliphatic thiols bonded to an aliphatic group such as methylene or ethylene having two or more SH groups are preferable. More preferably, they are polyfunctional aliphatic thiols having 4 or more SH groups. By increasing the number of functional groups, the polymerization initiation function is improved, and the surface of the pattern can be cured to near the substrate.

  As polyfunctional thiols, for example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bis thiopropio , Trimethylolpropane tristhioglycollate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethyl mercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dib Examples thereof include ethylamino) -4,6-dimercapto-s-triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

  These thiol chain transfer agents can be used alone or in combination of two or more.

  Further, the content of the thiol chain transfer agent is preferably 1 to 10% by mass, and more preferably 2.0 to 8.0% by mass in the total solid content of the photosensitive composition. In this range, the effect of the chain transfer agent is increased, and the sensitivity, the tapered shape, the wrinkles, the film shrinkage ratio, etc. become good.

<Solvent (E)>
The photosensitive composition for color filters of the present invention contains a solvent (E).
The coloring agent is sufficiently dispersed and infiltrated into the coloring agent carrier with a solvent, and the coloring film is easily formed on a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm. can do. Among them, organic solvents are preferred. The organic solvent is selected in consideration of the solubility of each component of the photosensitive composition as well as the safety, as well as the coating property of the photosensitive composition is good.

As the organic solvent, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1 2,4-butanediol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-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-dichloromethane Benzene, 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 monotertiary 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 glycol Methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone 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 Glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents may be used alone or in combination of two or more at an arbitrary ratio as needed.

  Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, ethylene glycol monomethyl ether, because of good dispersibility of colorant, permeability, and coatability of photosensitive composition. Acetate, ethylene glycol monoethyl ether acetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, 1,4-butanediol diacetate, acetate such as 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, and ethyl 3-ethoxypropionate.

  In addition, the organic solvent is used in an amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the coloring agent because it can adjust the photosensitive composition to an appropriate viscosity and form a colored film having an intended uniform film thickness. Is preferred.

<At least one selected from the group consisting of an antioxidant (F) and a polymerization inhibitor (G)>
The photosensitive coloring composition for color filters of the present invention contains at least one selected from the group consisting of an antioxidant (F) and a polymerization inhibitor (G) to prevent pattern peeling and pattern peeling, It can be set as the composition excellent in adhesiveness.
The antioxidant (F) and the polymerization inhibitor (G) will be described in detail below.

<Antioxidant (F)>
In the present invention, the "antioxidant" may be a compound having an ultraviolet absorbing function, a radical trapping function, or a peroxide decomposing function, and specifically, hindered phenol type or hindered amine type as an antioxidant. And phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylic acid ester, and triazine compounds, and known ultraviolet light absorbers, antioxidants and the like can be used. Further, the antioxidant used in the present invention is preferably one containing no halogen atom.

  Among these antioxidants, preferred are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants from the viewpoint of achieving both the transmittance and sensitivity of the coating film. Agents.

Examples of hindered phenolic antioxidants include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di) -Tert-Butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-tert-butyl-4-4 Nonylphenol, 2,2'-Isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-Butylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-thio- S- (6-t-Butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'-thiodiethyl bis- (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-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydro) And the like. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.
As a specific example, Adeka stub AO-20 made in ADEKA, AO-30, AO-40, AO50, AO60, AO 80, AO 320, KEMINOX 101, 179, 76, 9425 made by Chemipro, IRGANOX1010, 1035 made by BASF, Inc. 1076, 1098, 1135, 1330, 1726, 1425 WL, 1520 L, 245, 259, 3114, 5057, 565, and sianox CY-1790 and CY-2777 manufactured by Sun Chemical Co., Ltd., and the like.

As the hindered amine antioxidant, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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-butane tetracarboxylate, 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-triazine-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)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-Pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomeric types having a hindered amine structure And poly Mar-type compounds can also be used.
Specific examples thereof include Adekastab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, manufactured by ADEKA Corporation. LA-402F, LA-502XP, KAMISTAB 29, 62, 77, 29, 94 manufactured by Chemi-Pro Chemical Co., Ltd., Tinuvin 249, TINUVIN 111 FDL, 123, 144, 292, 5100, manufactured by BASF, Siersorb UV-3346, manufactured by Sun Chemical Co. -3529, UV-3853, and the like.

As a phosphorus antioxidant, tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 'isopropylidene diphenol alkyl phosphite, tris nonyl phenyl phosphite, tris dinonyl phenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-Di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidene bis (3-methyl-) 6-t-Butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxy phosphonyloxy)-Ben Zen, ethyl phosphite bis (2,4-di-tert-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.
Specific examples are Adekastab PEP-36, PEP-8, HP-10, Adekastab 2112, 1178, 1500, C, 3013, TPP manufactured by ADEKA Co., Ltd., IRGAFOS 168 manufactured by BASF, Hostanox P-EPQ manufactured by Clariant Chemicals Co., etc. Can be mentioned.

As a sulfur-based antioxidant, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 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 thereof include Adekastab AO-412S and AO-503 manufactured by ADEKA Co., Ltd., KEMINOXPLS manufactured by Chemi-Pro Chemical Co., Ltd., and the like.

As the benzotriazole-based antioxidant, compounds of oligomer type and polymer type having a benzotriazole structure can be used.
As a specific example, Adekastab LA-29, LA-31RG, LA-32, LA-36, -412S made by ADEKA Corporation, KEMISORB 71, 73, 74, 79, 279 made by Chemi-Pro Chemical Co., Ltd., TINUVIN PS made by BASF Corporation , 99-2, 384-2, 900, 928, 1130 and the like.

Examples of benzophenone antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4. -Octadecyloxy benzophenone, 2,2 'dihydroxy-4-methoxy benzophenone, 2,2'dihydroxy-4,4'-dimethoxy benzophenone, 2,2 ', 4,4'- tetrahydroxy benzophenone, 2-hydroxy-4 -Methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.
Specific examples thereof include Adekastab 1413 manufactured by ADEKA Co., Ltd., KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemi-Pro Chemical Co., Ltd., UV-12 manufactured by Sun Chemical Co., Ltd.

As a triazine type antioxidant, a 2, 4- bis (allyl) 6- (2-hydroxyphenyl) 1, 3, 5- triazine etc. are mentioned. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.
Specific examples thereof include Adekastab LA-46 and F70 manufactured by ADEKA Co., Ltd., KEMISORB 102 manufactured by Chemi-Pro Chemical Co., Ltd., TINUVIN 400, 405, 460, 477 and 479 manufactured by BASF, and Sieasorb UV-1164 manufactured by Sun Chemical Co., Ltd. .

  Examples of the salicylate-based antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate and the like. In addition, oligomer type and polymer type compounds having a salicylate structure can also be used.

  These antioxidants can be used alone or in combination of two or more at an arbitrary ratio as needed. Among antioxidants, contact holes are difficult to be blocked due to increased amount of initiator, and radicals Most preferred are hindered phenolic antioxidants that can capture more

It is preferable that the sum total of content of antioxidant (F) and the polymerization inhibitor (G) mentioned later is 0.1-5.0 mass% with respect to the total solid amount of a photosensitive coloring composition. By being in this range, pattern linearity is excellent, and chipping of the pattern is eliminated. More preferably, it is 1.0-3.0 mass%.
The photosensitive coloring composition for color filters 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 preferred from the viewpoint of pattern linearity.

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

  As a polymerization inhibitor, catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol , 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-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresor Alkyl resorcinol compounds such as cinol, 2-n-butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, 4-tert-butyl resorcinol, methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, tert-butyl hydroquinone, Alkyl hydroquinone compounds such as 2,5-di-tert-butyl hydroquinone, phosphine compounds such as tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, tribenzyl phosphine, trioctyl phosphine oxide, triphenyl phosphine oxide and the like Phosphine oxides such as triphenyl phosphite and tris nonyl phenyl phosphite Compounds, pyrogallol, and the like phloroglucinol.

  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 preferred. By being in this range, pattern linearity is excellent, and chipping of the pattern is eliminated. More preferably, it is 1.0-3.0 mass%.

<At least one selected from the group consisting of phosphoric acid ester compound (H) having an ethylenically unsaturated group and amino group-containing resin (I)>
The photosensitive coloring composition for color filters of the present invention contains at least one member selected from the group consisting of phosphoric acid ester compound (H) having an ethylenically unsaturated group and amino group-containing resin (I), It is possible to obtain a composition having excellent adhesion without causing pattern peeling or pattern peeling.
The phosphoric acid ester compound (H) having an ethylenically unsaturated group and the amino group-containing resin (I) will be described in detail below.

<Phoshate ester compound (H) having an ethylenically unsaturated group>
In the present invention, when the phosphoric acid ester has an ethylenically unsaturated group, even if the obtained photosensitive resin composition is cured with heat or light, the phosphoric acid ester does not bleed out and liquid crystal panel defects are generated. Suppress.
The phosphoric acid ester (H) having an ethylenically unsaturated group is a (meth) acrylate having a phosphoric acid ester group, an allyl compound, and more specifically, 2- (meth) acryloyloxyethyl acid phosphate, di- 2- (meth) acryloyloxyethyl phosphate, ethylene oxide modified phosphate dimethacrylate, 3- (meth) acryloyloxypropyl acid phosphate, di-3- (meth) acryloyloxypropyl acid phosphate, diphenyl (2-acryloyloxy ethyl phosphate Ethyl) phosphate, diphenyl (2-methacryloyloxyethyl) phosphate, phenyl (2-acryloyloxyethyl) phosphate, methacroyl oxyethyl acid phosphate monoethanolamine salt, 3-chloro-2-acylate Doth phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol methacrylate, (meth) acryloyloxy-2-hydroxypropyl acid phosphate, (meth) acryloyloxy-3-hydroxypropyl acid Examples include phosphate, (meth) acryloyloxy-3-chloro-2-hydroxypropyl acid phosphate, 2-methacryloxyethyl acid phosphate, allyl alcohol acid phosphate and the like.

  As commercially available products of these compounds, 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 (Made by Nippon Kayaku Co., Ltd.), MR-200, MR-260 (made by Daihachi Chemical Industry Co., Ltd.), etc. are mentioned.

Among them, in consideration of compatibility with an alkali-soluble resin, a phosphate ester compound containing ethylenic unsaturation represented by the following general formula (1) is preferable, and one kind may be used alone, or two or more kinds may be used in combination You may use it.
General formula (1)
[CH = CR ¹ -CO-O-X ¹ -O-CO-X ² -O] _n -PO- (OR ² ) _m
(In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. X ¹ and Each X ² independently represents an alkylene group which may 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 linear, branched and cyclic alkyl groups. Specifically, methyl group, ethyl group, normal propyl group, isopropyl Groups, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group and the like.

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

As the alkylene group which may have a substituent in X ¹ and X ² , a linear, branched or cyclic alkylene group may be mentioned. Specifically, a methylene group, an ethylene group, an isopropylene group, a cyclohexylene group And n-octyl and hexadecyl groups.

The X ^1, is preferably an unsubstituted alkylene group, more preferably an alkylene group having 1 to 4 carbon atoms, 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 which may be possessed is synonymous with the substituent in General formula (3).

  As a phosphoric acid ester compound containing ethylenic unsaturation represented by the said General formula (1), it is ethylene oxide modified | denatured phosphoric acid dimethacrylate preferably.

It is preferable that content of the phosphoric acid ester compound (H) which has an ethylenically unsaturated group is 0.1-5.0 mass% with respect to the total solid amount of a photosensitive coloring composition. By being in this range, the adhesion is excellent and pattern peeling is eliminated. More preferably, it is 0.5-2.0 mass%.
The photosensitive coloring composition for color filter of the present invention contains at least one selected from the group consisting of phosphoric acid ester compound (H) having an ethylenically unsaturated group and amino group-containing resin (I), It is preferable from the viewpoint of adhesion to include a phosphoric acid ester compound (H) having an ethylenically unsaturated group.

<Amino group-containing resin (I)>
Since the amino group-containing resin (I) has a site which interacts with the substrate to be coated, the adhesion is improved at the time of preparation of the color filter and the pattern peeling is eliminated. Specifically as the amino group-containing resin (I), polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid Alkylamine salts and long-chain polyaminoamide phosphates are used, and these can be used alone or in combination of two or more, but it is not necessarily limited thereto.

  Examples of commercially available amino group-containing resins include Dsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 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, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, 21116 or Lactimon, Lactimon-WS or Bykumen et al., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16 manufactured by Japan Lubrizol Corporation. 00, 17000, 18000, 20000, 20000, 21000, 24000, 26000, 28000, 31845, 32000, 32500, 32550, 33500, 32500, 34500, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500 etc., BASF · Japan-made EFKA-46, 47, 48, 452, 4008, 4010, 4015, 4020, 4047, 4050, 4050, 4060, 4800, 4401, 4402, 4403, 4406, 4408, 4300, 4310 , 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 750 , 7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB411, PB821, PB822, 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. By being in this range, the adhesion is excellent and pattern peeling is eliminated. It is 0.5-2.0 mass%.

<Thermosetting agent>
In the present invention, a thermosetting compound may be further included in combination with a thermoplastic resin which is a resin.
As the thermosetting compound, for example, an epoxy compound and / or a resin, a benzoguanamine compound and / or a resin, a rosin modified maleic acid compound and / or a resin, a rosin modified fumaric acid compound and / or a resin, a melamine compound and / or a resin Although a urea compound and / or resin, a phenol compound and / or resin are mentioned, this invention is not limited to this.

<Leveling agent>
It is preferable to add a leveling agent to the coloring composition for color filters 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 its main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie, and the like. As a specific example of dimethylsiloxane which has a polyester structure in a principal chain, BYK-310 by BYK-Chemie company, BYK-370, etc. are mentioned. The dimethylsiloxane having a polyether structure in the main chain and the dimethylsiloxane having a polyester structure in the main chain can also be used in combination. Generally, it is preferable to use 0.003 to 0.5% by mass of the leveling agent content in 100% by mass of the total mass of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a low solubility in water while having a hydrophilic group, and when it is added to a coloring composition, It is characterized by low surface tension reduction ability, and in addition to low surface tension reduction ability, it is useful that the wettability to the glass plate is good, and the addition amount at which defects of the coating film due to foaming do not appear. Those which can sufficiently suppress the chargeability can be preferably used. As a leveling agent which has such a preferable characteristic, dimethylpolysiloxane which has a polyalkylene oxide unit can use it preferably. The polyalkylene oxide unit may be a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit to dimethylpolysiloxane is a pendent type in which the polyalkylene oxide unit is bonded to a repeating unit of dimethylpolysiloxane, a terminal-modified type bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane It may be any of linear block copolymer types alternately and repeatedly bonded. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2203. -2-207, but not limited thereto.

The leveling agent may be supplemented with an anionic, cationic, nonionic or amphoteric surfactant. The surfactant may be used as a mixture of two or more.
Examples of anionic surfactants to be added to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Ester etc. are mentioned.

  Examples of the cationic surfactant added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. As a nonionic surfactant which is added to the leveling agent as auxiliaries, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines; 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 or the like, or an amine compound having a function of reducing dissolved oxygen in order to enhance the adhesion to a transparent substrate. It can be done.

  As the silane coupling agent, for example, vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, 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-ami Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, Aminosilanes such as 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 -2-ethylhexyl dimethylaminobenzoate, N, N-dimethyl paratoluidine etc. are mentioned.

<Method of producing photosensitive coloring composition for color filter>
The photosensitive coloring composition for color filters of the present invention comprises a colorant (A) in a colorant carrier such as a resin (B) and / or a solvent, preferably together with a dispersion aid, a kneader, a two-roll mill It can be finely dispersed and manufactured using various dispersing means such as 3-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular type bead mill or attritor (colorant dispersion). At this time, two or more kinds of colorants and the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed.
When the solubility of coloring agents such as dyes is high, specifically, the solubility in the solvent used is high, and if it is in a state where it is not dissolved by stirring and no foreign matter is observed, it is finely dispersed and manufactured as described above. There is no need.

  Moreover, when using as a photosensitive coloring composition for color filters (resist material), it can prepare as a solvent development type or an alkali development type coloring composition. A solvent-developable or alkali-developable coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, another pigment dispersant, and an additive. 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, it may contain a dispersing aid such as a resin-type dispersant, a dye derivative, a surfactant and the like as appropriate. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the coloring composition formed by dispersing the colorant in the colorant carrier using the dispersion aid has brightness and viscosity stability It becomes good.

[Resin type dispersant]
The resin type dispersant has a colorant affinity site having a property of adsorbing to the additive colorant, and a site compatible with the colorant carrier, and is adsorbed to the additive colorant and dispersed in the colorant carrier Work to stabilize the Specific examples of the resin type dispersant include polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt , Polysiloxane, long chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) with polyester having free carboxyl group, and salts thereof Etc., (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Water-soluble resin, water-soluble polymer compound, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

  As the dispersant used in the present invention, a polymer dispersant having a basic functional group is preferable, and a nitrogen atom-containing graft copolymer, a tertiary amino group in a side chain, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, etc. A nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant having a functional group containing The resin-type dispersant is preferably used in an amount of about 5 to 200% by weight based on the total amount of the colorant, and more preferably about 10 to 100% by weight from the viewpoint of film formability.

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

Moreover, as a resin type dispersing agent used by this invention, it is also preferable to contain following (S1) or (S2) as a resin type dispersing agent which has 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 tricarboxylic acid anhydride and / or 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 tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride Resin type dispersant which is united.

«Resin type dispersant (S1)»
The resin type dispersant (S1) can be produced by a known method such as WO 2008/007776, JP 2008-029901, JP 2009-155406 and the like. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at an end, and 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. Among them, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used because the terminal hydroxyl group is preferably plural.

  That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, has 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. 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 anhydride ring is opened to form a carboxylic acid. Produces

«Resin type dispersant (S2)»
The resin type dispersant (S2) can be produced by a known method such as JP2009-155406A, JP2010-185934A, JP2011-157416A, etc. For example, a compound having a hydroxyl group By polymerizing the ethylenically unsaturated monomer (r) in the presence of the reaction product of the hydroxyl group of (q) and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride can get. Among them, in the presence of a reaction product of a hydroxyl group of a compound (q1) having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride Preferably, it is a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing a monomer (r1).

  (S1) and (S2) are differences in whether the introduction of the polymer portion obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or later. Although molecular weight etc. may differ somewhat depending on various conditions, if the raw material and the reaction conditions are the same, theoretically the same one can be obtained.

[Dye derivative]
As dye derivatives used in the present invention, known dye derivatives having an acidic group, a basic group, a neutral group and the like in the organic dye residue can be used. For example, compounds having an acidic functional group such as sulfo group, carboxy group, phosphoric acid group and the like, amine salts thereof, compounds having a basic functional group such as a sulfonamide group or a tertiary amino group at the terminal, phenyl group or phthalimido The compound which has neutral functional groups, such as an alkyl group, is mentioned. JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP 2003-128669, JP 2004-091497, JP 2007-156395, JP 2008-094873, JP 2008-094986, JP 2008-095007, JP 2008 JP-195916-A, Patent No. 4585781-A, JP-2006-291194-A, JP-A-2007-226161, JP-A-2007-314681, JP-A-2007-314785, JP-A-2012-226110 JP-A-2017-165820 and JP-A-2005- 81383 JP, include known dye derivative according to such. In these documents, a dye derivative may be described as a derivative, a pigment derivative, a pigment dispersant or simply a compound, etc. However, the organic dye residue described above may be an acidic group, a basic group, a neutral group, etc. The compound which has a functional group of is synonymous with a pigment derivative. Moreover, these can be used individually or in mixture of 2 or more types.

  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, from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by mass or less, and more preferably 35 parts by mass or less.

[Surfactant]
As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; alkyl dimethylamino There may be mentioned amphoteric surfactants such as alkyl betaines such as betaine acetate and alkyl imidazolines, which may be used alone or in combination of two or more, but it is not necessarily limited thereto.

  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. When the content of the surfactant is less than 0.1 parts by mass, the added effect is difficult to be obtained, and when the content is more than 55 parts by mass, the dispersing agent may affect the dispersion due to an excess of the dispersing agent. .

<Removal of coarse particles>
The coloring composition of the present invention may be coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, filtration with a sintered filter or membrane filter, and the like. It is preferable to carry out the removal of the mixed dust. Thus, the coloring composition preferably contains substantially no particles 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 comprising at least one filter segment formed of the coloring composition for color filters 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 comprises the coloring composition for color filters of the present invention. Preferably, it is formed using.

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

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

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured using a TSK gel column (manufactured by Tosoh Corporation) and a GPC equipped with a RI detector (HLC-8120GPC manufactured by Tosoh Corporation), using polystyrene as the developing solvent and polystyrene conversion It is a weight average molecular weight (Mw).

<Method for producing resin solution>
(Resin solution (B-1))
Add 100 parts of propylene glycol monomethyl ether acetate to a reaction vessel equipped with a separable 4-neck flask, a thermometer, a condenser, a nitrogen gas inlet pipe, and a stirrer, and heat it at 120 ° C while injecting nitrogen gas into the vessel. 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 from the dropping tube at a temperature The reaction mixture was added dropwise over 2.5 hours to carry out the polymerization reaction.
Next, the inside of the flask is replaced with air, and 17.0 parts of acrylic acid and 0.3 parts of trisdimethylaminomethylphenol as a catalyst required for the reaction of the precursor at this stage and 0.3 parts of hydroquinone are charged, The reaction was carried out for 5 hours to obtain a resin solution having a weight average molecular weight of about 12,000. The introduced acrylic acid is ester-bonded to the epoxy group terminal of the glycidyl methacrylate structural unit, so that no carboxyl group is generated in the resin structure.
Further, 0.5 parts of triethylamine was added as a catalyst required for the reaction of 30.4 parts of tetrahydrophthalic anhydride and the precursor in this stage, and the reaction was carried out at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of two carboxyl groups formed by cleavage of the carboxylic acid anhydride is ester-bonded to a hydroxyl group in the resin structure, and the other forms a carboxyl group terminal, and the weight average molecular weight is about 13 2000 resin solutions were obtained.
Propylene glycol monomethyl ether acetate was added such that the nonvolatile content was 20%, to obtain a resin solution (B-1).

  The weight ratio of the structural unit in the resin solution (B-1) is tetrahydrophthalic anhydride as the structural unit; 22.0% by mass, styrene: 15.0% by mass, dicyclopentanyl methacrylate; 29.3% by mass, glycidyl The sum of methacrylate and acrylic acid esterified to its glycidyl end; 37.4% by mass.

(Resin solution (B-2))
Charge 70.0 parts of propylene glycol monoethyl ether acetate into a separable 4-neck flask equipped with a thermometer, a condenser, a nitrogen gas inlet pipe, a dropping pipe, and a stirring device, raise the temperature to 80 ° C, After substitution, 3.8 parts of methacrylic acid, 4.1 parts of 2-hydroxyethyl methacrylate, 7.4 parts of benzyl methacrylate, paracumylphenol ethylene oxide-modified acrylate (manufactured by Toagosei Co., Ltd. "Alonix M-" from the dropping tube A mixture of 7.4 parts of 110 ′ ′ and 0.4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 30,000.
After cooling to room temperature, approximately 2 parts of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and propylene glycol mono is used so that non-volatile content is 20% by mass in the resin solution Ethyl ether acetate was added to obtain a resin solution (B-2) which is an alkali-soluble resin.

(Resin solution (B-3))
Add 100 parts of propylene glycol monomethyl ether acetate to a reaction vessel equipped with a separable 4-neck flask, a thermometer, a condenser, a nitrogen gas inlet pipe, and a stirrer, and heat it at 120 ° C while injecting nitrogen gas into the vessel. 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 from the dropping tube at a temperature The mixture of parts was dropped for 2.5 hours to carry out the polymerization reaction.
Next, the inside of the flask is replaced with air, 19.7 parts of glycidyl methacrylate and 0.3 parts of trisdimethylaminomethylphenol as a catalyst required for the reaction of the precursor at this stage, and 0.3 parts of hydroquinone are charged, 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 such that the nonvolatile content was 20%, to obtain a resin solution (B-3).
The weight ratio of the structural units in the resin solution (B-3) was 13.0% by mass of acrylic acid, 53.0% by mass of benzyl methacrylate, 13% by mass of dicyclopentanyl methacrylate, and esterified with acrylic acid terminal Glycidyl methacrylate: 21.0% by mass.

(Resin solution (B-4))
In a flask equipped with a condenser and a stirrer, 3 parts of 2,2'-azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate are charged, and then 1,2,2,6,6-pentamethyl piperidyl methacrylate 1 Parts, 15 parts of methacrylic acid, 34 parts of 2-hydroxyethyl methacrylate, 20 parts of N-phenylmaleimide, 15 parts of styrene, 10 parts of benzyl methacrylate, 5 parts of n-butyl methacrylate and 2,4-diphenyl-4-4 as a molecular weight modifier Five parts of methyl-1-pentene (manufactured by NOF Corp., trade name: Nofmer MSD) were charged and purged with nitrogen. After stirring gently, the temperature of the reaction solution was raised to 80 ° C., and the temperature was kept for 5 hours for polymerization to obtain an acrylic resin solution with a weight average molecular weight of 12,500. After cooling to room temperature, about 2 g of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and propylene glycol monoethyl so that the non-volatile content is 20% by mass in the resin solution synthesized above. 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 condenser 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 are charged, and subsequently 15 parts by mass of methacrylic acid, succinic acid monobasic 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), After purging with nitrogen, the reaction solution was heated to 80 ° C. with gentle stirring, and polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution is raised to 100 ° C., 0.5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) is added, and the polymerization is further 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, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and propylene glycol monoethyl so that the non-volatile content is 20% by mass in the resin solution synthesized above. Ether acetate was added to obtain a resin solution (B-5) which is an alkali-soluble resin.

<Production of amino group-containing resin>
(Production of Amine Group-Containing Resin (I-1))
In a reaction vessel equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, 39.2 parts of methoxypropyl acetate were charged, and the temperature was raised to 110 ° C. while replacing with nitrogen. In a reaction vessel, 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, and stirred until uniform. It reacted for 3 hours at the same temperature after that. Thus, a resin-type dispersant solution having an amine value of 67.8 mg KOH / g and a weight average molecular weight of 9,000 (Mw) per solid content 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 is 40 mass%. (I-1) was obtained.

<Manufacture of micronized pigment>
(Red finely divided pigment (R-1))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 ("IRGAZIN RED 2030" manufactured by BASF Corporation), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 80 ° C for 6 hours. Next, this kneaded material is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , 190 parts of a finely divided red pigment (R-1) were obtained.

(Red finely divided 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 Co., Ltd.) and kneaded at 80 ° C. for 6 hours. Next, this kneaded material is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , 190 parts of a finely divided red pigment (R-2) were obtained.

(Red finely divided pigment (R-3))
Diketopyrrolopyrrole red pigment C.I. I. Pigment red 254, C.I. I. A red finely divided pigment (R-3) was obtained in the same manner as the red finely divided pigment (R-1) except that the pigment red 177 was substituted.

(Yellow micronized pigment (Y-1))
Diketopyrrolopyrrole red pigment C.I. I. Pigment red 254 as a yellow pigment C.I. I. Pigment Yellow 138 (BASF "PAliotol Yellow L 0962 HD"), except that it was changed to a red finely divided pigment (R-1), to obtain a finely divided yellow pigment (Y-1).

(Yellow micronized pigment (Y-2))
Diketopyrrolopyrrole red pigment C.I. I. Pigment red 254 as a yellow pigment C.I. I. A yellow finely divided pigment (Y-2) was obtained in the same manner as the red finely divided pigment (R-1) except that Pigment Yellow 150 ("E-4GN" manufactured by LANXESS Corporation) was used.

(Yellow micronized pigment (Y-3)
According to the synthesis method described in Example 8 of JP 2012-226110 A, the quinophthalone compound (b) was synthesized to obtain a yellow pigment 1.
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 A yellow finely divided pigment (PY-3) was obtained in the same manner as the red finely divided pigment (R-1) except that the obtained yellow pigment 1 was substituted.

(Green micronized pigment (G-1))
Diketopyrrolopyrrole red pigment C.I. I. The green finely divided pigment (G-1) is prepared in the same manner as the red finely divided pigment (R-1) except that the pigment red 254 is replaced with a halogenated zinc phthalocyanine green pigment (C.I. pigment green 58). Obtained.

(Green micronized pigment (G-2))
In a three-necked flask, 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 are added and heated to 90.degree. The mixture was allowed to react for 8 hours. After cooling 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 A green finely divided pigment (G-2) was obtained in the same manner as the red finely divided pigment (R-1) except that the obtained green pigment 1 was substituted.

(Green micronized pigment (G-3))
In a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following chemical formula (5), 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) are added and stirred: The reaction was allowed to proceed at 20 ° C. for 6 hours. Thereafter, the reaction mixture was poured into 5,000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. In a beaker, 500 parts of 2.5% aqueous sodium hydroxide solution and the collected residue were added and stirred at 80 ° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water and dried to obtain a pigment in which an average of 10.1 bromine atoms was 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 is substituted on the obtained phthalocyanine ring, and 13.9 parts of diphenyl phosphate are added. The mixture was heated to ° C and allowed to react for 8 hours. After cooling 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 A green finely divided pigment (G-3) was obtained in the same manner as the red finely divided pigment (R-1) except that the obtained green pigment 2 was substituted.

Chemical formula (5)

(Blue finely divided 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 a dispersant represented by the chemical formula (6) are added, and after stirring at 30 ° C. for 2 hours, 5000 parts of It mixed with water and obtained the aqueous solution which copper phthalocyanine particle precipitated. The resulting aqueous solution was stirred for 30 minutes, filtered, washed with water, dried and pulverized to obtain 95 parts of a blue finely divided pigment (B-1).

Chemical formula (6)

(Blue finely divided pigment (B-2))
85 parts of crude copper phthalocyanine synthesized by a known method, 15 parts of a dispersant represented by the chemical formula (6), 1000 parts of sodium chloride and 280 parts of diethylene glycol are charged in a stainless steel 1 gallon kneader manufactured by Inoue Manufacturing Co. did. After kneading, it was taken out in 20000 parts of a 45 ° C. aqueous solution of acetic acid-sodium acetate (pH 4.0), stirred for 1 hour while keeping warm, filtered, washed with water, dried and ground to obtain 96 parts of a finely divided blue pigment .

(Blue finely divided pigment (B-3))
95 parts of ε-type copper phthalocyanine pigment “LIONOL BLUE E” manufactured by Toyo Color Co., Ltd., 5 parts of a dispersant represented by the chemical formula (6), 1000 parts of sodium chloride and 280 parts of diethylene glycol are charged in a stainless steel 1 gallon kneader manufactured by Inoue Seisakusho And kneading at 80 ° C. for 10 hours. After kneading, it was taken out in 20000 parts of a 30 ° C. aqueous buffer solution of acetic acid-sodium acetate (pH 4.0), stirred for 1 hour while keeping warm, filtered, washed with water, dried and ground to obtain 96 parts of a blue finely divided pigment (B-3) .

(Purple micronized pigment (V-1))
Dioxazine purple pigment C.I. I. Pigment Violet 23 (PV23) ("Fast Violet RL" manufactured by Clariant), 500 parts of sodium chloride, and 250 parts of polyethylene glycol (manufactured by Tokyo Kasei Co., Ltd.) are charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) It knead | mixed for 12 hours at 120 degreeC. Next, this mixture is poured into about 5 liters of warm water and stirred with a high speed mixer for about 1 hour while heating to about 70 ° C. to form a slurry, and then filtered and washed with water to remove sodium chloride and diethylene glycol, The whole was dried at 80 ° C. overnight to obtain a purple finely divided pigment (V-1).

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

<Production of pigment dispersant>
(Pigment dispersant solution (K-1))
100 parts of methyl methacrylate, 100 parts of n-butyl acrylate and 40 parts of propylene glycol monomethyl ether acetate are charged as a first stage synthesis in a reaction vessel equipped with a gas introduction pipe, a condenser, a stirring blade and a thermometer. Replaced by The reaction vessel is heated to 80 ° C., 12 parts of 3-mercapto-1,2-propanediol are added, and 0.2 parts of 2,2′-azobisisobutyro nitrile is divided into 20 portions to 30 It was added every minute and reacted at 80 ° C. for 12 hours, and solid content measurement confirmed that 95% was reacted.
Next, as a 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 It was added and allowed to react 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. Thus, an acidic resin type pigment dispersant having an aromatic carboxyl group and a poly (meth) acrylate skeleton having an acid value of 42 mg KOH / g per solid content and a non-volatile content of weight average molecular weight 9,800 of 40% by mass A solution (K-1) was obtained.

<Production of pigment dispersion>
(Pigment dispersion (PR-1))
After uniformly mixing 14.0 parts of the red finely divided pigment (R-1), 15.0 parts of the pigment dispersant solution (K-1), and 71.0 parts of ethylene glycol monomethyl ether acetate (PGMAC) After dispersing for 3 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads of 0.5 mm in diameter, filter with a 5 μm filter to obtain a pigment dispersion of PR254 (PR-1) Got).

(Pigment dispersions PR-2 to 5, PY-1 to 3, PG-1 to 3, PB-1 to 3, PV-1, dye solution DV-1)
Pigment dispersions PR-2 to 5, PY-1 to 3, PG-, in the same manner as the pigment dispersion PR-1 except that the colorant, the pigment dispersant solution, and the organic solvent are changed to the compositions shown in Table 1. 1 to 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: EFKA 4300 (manufactured by BASF): Basic resin type dispersant (corresponding to amino group-containing resin (I))

<Production of Photosensitive Colored Composition for Color Filter>
Example 1
(Photosensitive coloring composition (RE-1))
After stirring and mixing the mixture of the following composition so that it might become uniform, it filtered with a 1.0 micrometer filter, and produced coloring 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 the photosensitive coloring composition (RE-1) except that the compositions and the blending amounts shown in Tables 2 to 7 were changed.

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

(Pattern damage evaluation)
The resulting photosensitive coloring composition is coated on a 100 mm × 100 mm, 0.7 mm glass substrate to a film thickness of 2.5 μm, and passed through a linear mask of 50 μm width and 500 μm length for 40 mJ / cm ² UV exposure was performed under the conditions. Thereafter, the potassium hydroxide developer was sprayed by spraying to remove the uncured portion, and a desired pattern was formed. The obtained coating film is subjected to heat treatment (post-baking) in an oven at 230 ° C. for 40 minutes, and ten linear patterns obtained on a microscope (“BX-51” manufactured by Olympus Optical Co., Ltd.) are multiplied by 10 When the edge of the line was depressed, it was judged as a chip and the number of missing was confirmed. According to the number of omissions (chips), it evaluated as follows. The film thickness of the coating film was measured using Dektak 8 (manufactured by Japan Vacuum Technology Co., Ltd.).
:: no nicks in the pattern 〇: 1 to 3 nicks in the pattern △: 4 to 20 nicks in the pattern ×: 21 or more

(Pattern peeling evaluation)
The resulting photosensitive coloring composition is coated on a 100 mm × 100 mm, 0.7 mm glass substrate to a film thickness of 2.5 μm, and passed through 75 10 μm × 50 μm rectangular masks under a condition of 40 mJ / cm ² . UV exposure was performed. Thereafter, the potassium hydroxide developer was sprayed by spraying to remove the uncured portion, and a desired pattern was formed. About the obtained coating film, the heat processing (post-baking) were performed for 40 minutes in a 230 degreeC oven, and the peeling of the pixel was confirmed with the microscope ("Oxton-Optical Co., Ltd. make" BX-51 "). The evaluation was performed by calculating the number of peeling of the 75 10 μm × 50 μm rectangular pixels formed on the glass substrate, and was evaluated based on the following criteria. The film thickness of the coating film was measured using Dektak 8 (manufactured by Japan Vacuum Technology Co., Ltd.).
:: no pattern peeling / in 75 pieces 個: 1 to 5 pieces in 75/75 pieces of pattern △: 5 to 10 pieces out of 75 pieces in pattern ×: 11 or more pieces in 5 or more pieces of pattern During ~

(Evaluation of contact holes)
The resulting photosensitive coloring composition is coated on a 100 mm × 100 mm, 0.7 mm glass substrate to a film thickness of 2.5 μm, and passed through a mask having a pattern with an opening diameter of φ 30 μm under a condition of 40 mJ / cm ² . UV exposure was performed. Thereafter, the potassium hydroxide developer was sprayed by spraying to remove the uncured portion, and a desired pattern was formed. About the obtained coating film, the heating process (post-baking) was performed for 40 minutes in a 230 degreeC oven, and the contact hole of the pixel was confirmed with the microscope ("BX-51" by Olympus optical company make). In the evaluation, the shape of the contact hole and whether it was closed were visually observed and evaluated according to the following criteria. The film thickness of the coating film was measured using Dektak 8 (manufactured by Japan Vacuum Technology Co., Ltd.).
:: The shape of the contact hole is circular :: 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.

<Photoinitiator (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 ("IRGACURE 907" manufactured by BASF Corp.)

<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 Industry Co., Ltd.)

<Photopolymerizable monomer (C)>
C-1: Dipentaerythritol hexaacrylate ("Toronoke Synthesis" ALONIX M-402 ")
C-2: trimethylolpropane triacrylate ("Alonics M-309" manufactured by Toagosei Co., Ltd.)
C-3: trimethylolpropane EO-modified triacrylate ("Alonix M-350" manufactured by Toagosei Co., Ltd.)
C-4: trimethylolpropane PO modified triacrylate ("Alonix M-310" manufactured by Toagosei Co., Ltd.)
C-5: pentaerythritol tetraacrylate ("Alonics M-450" manufactured by Toagosei Co., Ltd.)
C-6: Ethoxylated isocyanurate triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. "A-9300")
C-7: dipentaerythritol pentaacrylate hexamethylene diisocyanate (reactant of dipentaerythritol pentaacrylate and hexamethylene diisocyanate)
C-8: pentaerythritol triacrylate hexamethylene diisocyanate C-9: polyfunctional urethane acrylate (CASM "KUA-4I")

<Antioxidant (F)>
(Phenolic antioxidant)
F-1: 2 pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (BASF "IRGANOX 1010")
F-2: Thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (BASF "IRGANOX 1035")
F-3: Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ("IRGANOX 1076" manufactured by BASF Corporation)
F-4: benzene propanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester (manufactured by BASF "IRGANOX 1135")

(Phosphoric acid antioxidant)
F-5: Tris (2,4-di-tert-butylphenyl) phosphite ("IRGAFOS 168" manufactured by BASF)
F-6: acrylic acid 1′-hydroxy [2,2′-ethylidenebis [4,6-bis (1,1-dimethylpropyl) benzene]]-1-yl (Sumitomo Chemical Corporation “SUMIKIZER (R) GS ")
F-7: Acrylic acid 1′-hydroxy [2,2′-methylenebis (4-methyl-6-tert-butylbenzene)]-1-yl (“SUMILIZER (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) ("SUMILIZER (R) GA-80" manufactured by Sumitomo Chemical Co., Ltd.)

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

<Polymerization inhibitor (G)>
G-1: methyl hydroquinone (manufactured by SEIKO CHEMICAL Co., Ltd. "MH")

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

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

・ Organic solvent: PGMAC

  It consists of at least one member 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) It is a photosensitive coloring composition for color filters containing at least 1 type chosen from a group, Comprising: Content of a coloring agent (A) is 25 mass%-45 with respect to solid content whole quantity in the photosensitive coloring composition for color filters The photosensitive coloring composition for color filters which is mass% and whose content of a photopolymerization monomer (C) is 30 mass%-55 mass% with respect to solid content whole quantity in the photosensitive coloring composition for color filters By using this method, it was possible to form a circular contact hole without pattern peeling 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 an antioxidant (F) and a polymerization inhibitor (G), or a phosphoric acid ester compound (H) having an ethylenically unsaturated group (amino acid containing resin (I Or at least one selected from the group consisting of and the content of the photopolymerization monomer (C) is 30% by mass to 55% by mass with respect to the total solid content in the photosensitive coloring composition for color filter If the content of the coloring agent (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 color filters A lot of pattern burrs and pattern peelings were observed, and the contact hole shape was also distorted or blocked.

  Therefore, it is possible to form a circular contact hole without pattern peeling and pattern peeling, and to prepare a colored composition having an excellent resolution.

  Furthermore, when the same evaluation was performed on a color filter produced using the above-mentioned coloring composition, favorable results were obtained in pattern peeling and pattern peeling, and high-yield production could be performed. As a result, the liquid crystal display device, the solid-state imaging device, and the organic EL display device using the color filter can be suitably used.

Claims (7)

Photosensitivity for color filter including coloring agent (A), resin (B) (except resin (I)), photopolymerizable monomer (C), photopolymerization initiator (D) and solvent (E) A coloring composition,
Furthermore, it comprises at least one member 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) And at least one selected from the group consisting of
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 color filters, and the content of the photopolymerizable monomer (C) is The photosensitive coloring composition for color filters which is 30 to 55 mass% with respect to the solid content whole quantity of the photosensitive coloring composition for color filters.   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 based on the total solid content of the photosensitive coloring composition for color filter The photosensitive coloring composition for color filters as described in item 1. 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 amount of solids in the photosensitive coloring composition for color filter,
The content of amino group containing resin (I) is 0.1 mass% or more and 5.0 mass% or less with respect to solid content whole quantity of the photosensitive coloring composition for color filters of Claim 1 or 2 Photosensitive coloring composition for color filters.   The photosensitive coloring composition for color filters of any one of Claims 1-3 containing the phosphoric acid ester compound (H) which has antioxidant (F) and an ethylenically unsaturated group.   The antioxidant (F) is a phenolic antioxidant, The photosensitive coloring composition for color filters of any one of Claims 1-4. The phosphoric acid ester compound (H) which has an ethylenically unsaturated group is a phosphoric acid ester compound represented by following General formula (1), Photosensitive coloration for color filters of any one of Claims 1-5 Composition.
General formula (1)
[CH = CR ¹ -CO-O-X ¹ -O-CO-X ² -O] _n -PO- (OR ² ) _m
(In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. X ¹ and Each X ² independently represents an alkylene group which may have a substituent, m is an integer of 0 to 2, and n is an integer of 1 to ^3. )   The color filter which comprises the filter segment formed from the photosensitive coloring composition for color filters of any one of Claims 1-6 on a board | substrate.