JP2022178749A - Photosensitive coloring composition, color filter, image display device, and solid state image sensor - Google Patents

Abstract

To provide a photosensitive coloring composition having excellent developability, adhesion, and pattern profile.SOLUTION: A photosensitive coloring composition contains a colorant (A), a basic dispersant (B), a binder resin (C), a polymerizable monomer (D), and a photopolymerization initiator (E). The binder resin (C) includes a binder resin (C1) containing a polymerizable unsaturated group. The polymerizable monomer (D) includes a polymerizable monomer (D1) containing a fluorene skeleton and having a glass transition temperature of 200°C or lower.SELECTED DRAWING: Figure 1

Description

The present invention provides a color liquid crystal display device, a color solid-state imaging device, an organic EL display device, a quantum dot display device, and a coloring composition used in the manufacture of a color filter used in electronic paper and the like, and a photosensitive coloring composition, and a color filter having filter segments formed using the same.

The color filter is formed by arranging two or more fine band-shaped filter segments with different hues in parallel (stripe) or crossing each other on a transparent substrate such as a glass substrate, or are arranged so as to be arranged in order in each of the vertical and horizontal directions. The filter segments have small dimensions of several microns to several hundred microns, and are orderly arranged in a predetermined array for each hue.

At present, as a method for producing a color filter, a process of applying a photosensitive coloring composition to a transparent substrate such as glass and drying it to remove the solvent from the coating film, followed by forming the coating film into a photo film having a desired pattern shape. A step of irradiating and curing ultraviolet rays or the like through a mask (hereinafter referred to as exposure), followed by a step of washing and removing the unexposed portion of the coating film (hereinafter referred to as development), and then, if necessary, the cured film is sufficiently removed. A first-color filter segment pattern is obtained by a heat treatment (hereinafter referred to as post-baking) step for hardening the resin. By performing the same operation, filter segment patterns of other colors are formed to complete the color filter.

In recent years, the area per pixel tends to decrease due to the miniaturization of image display devices and solid-state imaging devices and the increase in the number of pixels. Also, higher definition of patterns is required. However, when the concentration of the coloring agent is increased, the transmittance of ultraviolet rays into the film is lowered, thereby degrading the degree of curing and reducing the adhesion to the substrate. In particular, the adhesion deteriorates when the pattern is made highly fine. Further, when the amount of the photopolymerization initiator is increased in order to increase the degree of curing, there is a problem that the pattern becomes thicker than the desired line width and the shape deteriorates.

Various methods have been examined so far to solve these problems. Patent Document 1 discloses a photosensitive coloring composition containing a polyalkylene oxide or an alkylene oxide adduct of glycerin.

JP 2007-058192 A

An object of the present invention is to provide a photosensitive coloring composition which is excellent in developability, adhesion and pattern shape.

The present invention is a photosensitive coloring composition comprising a coloring agent (A), a basic dispersant (B), a binder resin (C), a polymerizable monomer (D), and a photopolymerization initiator (E), Polymerization in which the binder resin (C) contains a binder resin (C1) containing a polymerizable unsaturated group, and the polymerizable monomer (D) contains a fluorene skeleton and has a glass transition temperature of 200° C. or less It relates to a photosensitive coloring composition containing a photosensitive monomer (D1).

Moreover, this invention relates to the said photosensitive coloring composition whose content of the said polymerizable monomer (D1) is 50 mass % or more in 100 mass % of polymerizable monomers (D).

Further, in the present invention, the content of the photopolymerization initiator (E) is 0.00 with respect to the total mass of the binder resin (C1) containing the polymerizable unsaturated group and the polymerizable monomer (D). 5 to 10% by mass, it relates to the photosensitive coloring composition.

The present invention also relates to the photosensitive coloring composition, wherein the polymerizable unsaturated group-containing binder resin (C1) contains at least two binder resins having different weight average molecular weights.

Further, in the present invention, the binder resin (C1) containing a polymerizable unsaturated group is a binder resin (C1-1) containing a polymerizable unsaturated group having a weight average molecular weight of 12,000 or less and a weight average molecular weight of 18,000. It relates to the photosensitive coloring composition containing the binder resin (C1-2) containing the above polymerizable unsaturated groups.

The present invention also provides a binder resin (C1-1) containing a polymerizable unsaturated group having a weight average molecular weight of 12,000 or less and a binder resin (C1-1) containing a polymerizable unsaturated group having a weight average molecular weight of 18,000 or more. -2) in a mass ratio of 20:80 to 80:20.

The present invention also relates to the photosensitive coloring composition, wherein the photopolymerization initiator (E) contains an oxime compound (E1).

The present invention also relates to the above photosensitive coloring composition, further comprising an acidic dispersant (F).

The present invention also relates to a color filter comprising a substrate and a filter segment formed from the photosensitive coloring composition.

The present invention also relates to an image display device including the color filter.

The present invention also relates to a solid-state imaging device comprising the above color filter.

According to the present invention, it is possible to provide a photosensitive coloring composition excellent in developability, adhesion, pattern shape and solvent resistance. Moreover, the present invention can provide a color filter, an image display device, and a solid-state imaging device.

FIG. 1 is a schematic cross-sectional view of a liquid crystal display device.

Each constituent component of the photosensitive coloring composition of the present invention is described below.
In the present application, when "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide""acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively, unless shall be represented.
Moreover, "C.I." mentioned in this specification means a color index (C.I.).

<Colorant (A)>
The photosensitive coloring composition of the present invention contains a coloring agent (A).

The coloring agent (A) is not particularly limited, and may be either a pigment or a dye, and can be used in combination. Pigments are preferred because color filters are required to have light resistance, heat resistance, and solvent resistance.

(pigment)
Pigments are not particularly limited, and examples thereof include compounds classified as pigments in the Color Index.

Specific examples of red pigments that can be used in the present invention include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3,57,57:1,57:2,58:4,60,63,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81: 3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276,277,278,279,280, 281,282,283,284,285,286,287,291,295,296, pigments described in JP-A-2014-134712, pigments described in Japanese Patent No. 6368844, and the like. Among these, from the viewpoint of heat resistance, light resistance and transmittance, C.I. I. Pigment Red 48: 1,122,177,224,242,269,254,291,295,296, the pigment described in JP-A-2014-134712, the pigment described in Patent No. 6368844 is preferable, C. I. Pigment Red 177, 254, 291, 295, 296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844 are particularly preferred.

Specific examples of orange pigments that can be used in the present invention include C.I. I. Pigment Orange 36, 38, 43, 64, 71, 73 and the like.

Specific examples of yellow pigments that can be used in the present invention include C.I. I. Pigment Yellow 1,2,3,4,5,6,10,12,13,14,15,16,17,18,24,31,32,34,35,35:1,36,36:1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and pigments described in JP-A-2012-226110. Among these, C.I. I. Pigment Yellow 138, 139, 150, 185, 231, 233 and the pigments described in JP-A-2012-226110 are preferred.

Specific examples of green pigments that can be used in the present invention include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 and the like. Among these, C.I. I. Pigment Green 36, 58, 59, 62, 63 are preferred.

Specifically, the blue pigment that can be used in the present invention is 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, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 are preferred.

Specifically, the purple pigment that can be used in the present invention is C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, C.I. I. Pigment Violet 19, 23 are preferred.

Specifically, the black pigment that can be used in the present invention is C.I. I. Pigment Black 1, 6, 7, 12, 20, 31 and the like.

An inorganic pigment can also be used as the coloring agent (A) in the photosensitive coloring composition of the present invention. For example, titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, amber, synthetic iron black, etc. is mentioned.

(dye)
Dyes are not particularly limited, and examples thereof include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Moreover, it may be in the form of a derivative of these or a lake pigment obtained by turning a dye into a lake.

Furthermore, in the case of acid dyes having an acidic group such as sulfonic acid or carboxylic acid, or in the form of direct dyes, inorganic salts of acid dyes, acid dyes and quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, Alternatively, a salt-forming compound with a nitrogen-containing compound such as a primary amine compound, or a salt-forming compound using a resin component having these functional groups, or a sulfonamidation and use as a sulfonic acid amide compound. In order to be excellent in resistance, it is possible to make a coloring composition excellent in fastness, which is preferable.
In addition, a salt-forming compound of an acid dye and a compound having an onium base is also preferable because of excellent fastness, and more preferably, the compound having an onium base is a resin having a cationic group in its side chain.

In the case of the form of a basic dye, it can be used by forming a salt using an organic acid, perchloric acid, or a metal salt thereof. Among them, salt-forming compounds of basic dyes are preferable because of their excellent resistance and compatibility with pigments. An anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound obtained by forming a salt with an acid dye can be used. It is more preferable.

Further, when the dye skeleton has a polymerizable unsaturated group, the dye can be excellent in resistance, which is preferable.

Chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, etc.). dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinone imine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes Dyes, polymethine 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, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof. , but not particularly limited to these.

Among these dye structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium Xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanines. A dye structure derived from a dye selected from the group of dyes is more preferable. Specific dye compounds capable of forming a dye structure are described in "Shinban Dye Handbook" (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and Colorists), "Dye Handbook" (Ogawara et al.). Ed.; Kodansha, 1986).

Colorant (A) can be used alone or in combination of two or more.

The content of the coloring agent (A) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on 100% by mass of the non-volatile matter of the photosensitive coloring composition.

(Refinement of pigment)
It is preferable to use the pigment after miniaturization. The method of refining is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution-precipitation can be used. Among these, the salt milling treatment by the kneader method, which is one type of wet grinding, is preferable. The average primary particle size of the finely divided pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoint of dispersibility and contrast ratio, the average primary particle size is more preferably 10 to 70 nm.

The salt milling process involves milling a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent while heating using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, and sand mill. This is a treatment in which water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water after kneading to a certain extent. The water-soluble inorganic salt functions as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate and the like, and sodium chloride (salt) is preferred from the viewpoint of cost. The amount of the water-soluble inorganic salt to be used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass, based on 100 parts by mass of the pigment, in terms of both processing efficiency and production efficiency.

The water-soluble organic solvent has the function of moistening the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible in) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.

If necessary, a resin may be added to the salt milling treatment. By adding a resin, the pigment is coated with the resin, and stability, light resistance, etc. are improved. The type of the resin is not particularly limited, and includes natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like. Among these, it is preferable that they are solid at room temperature, insoluble in water, and partially soluble in the above organic solvents. The amount of the resin to be added is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the pigment.

<Basic dispersant (B)>

A known basic dispersant (B) can be used in the photosensitive coloring composition of the present invention. The basic dispersant (B) has a colorant-affinity site having a property of adsorbing to the added colorant and a site compatible with the colorant carrier. Specific examples include urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids ( Part) Amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, poly(lower alkyleneimine) and liberation Oil-based dispersants such as amides and salts thereof formed by reaction with a polyester having a carboxyl group, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, Water-soluble resins such as styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphate esters, etc. are used. These can be used alone or in combination of two or more.
Examples of polymeric dispersants having basic functional groups include nitrogen atom-containing graft copolymers and nitrogen atom-containing polymers having functional groups containing tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. in side chains. Examples include acrylic block copolymers and urethane polymer dispersants.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by BYK-Japan. or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, Lactimon, Lactimon-WS or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940 manufactured by Lubrizol Japan 、１６０００、１７０００、１８０００、２００００、２１０００、２４０００、２６０００、２７０００、２８０００、３１８４５、３２０００、３２５００、３２５５０、３３５００、３２６００、３４７５０、３５１００、３６６００、３８５００、４１０００、４１０９０、５３０９５、５５０００、５６０００、７６５００ Etc., EFKA-46, 47, 48, 452, 4008, 4060, 4406, 4408, 450, 451, 453, 4540, 4800, 5070, 7500, 7554, 1101, 120, 150, 1502, Efka PU manufactured by BASF 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4061, 4063, 4080, Efka PA 4400, 4401, 4402, 4403, 4414, 4450, Efka PX 4300, 4310, 4320, 4330, 45340, 4700, 4701, 4731, 4732, Efka FA4610, 4665, 4666, Dispex Ultra PA 4501, 4503, 4550, 4560, 4580, 4590, Ajinomoto Fine-Techno Co., Ltd. Ajispa-PA111, PB711, PB821, PB822, PB824, etc. mentioned.

A resin-type dispersant having a carboxyl group can be suitably used in the photosensitive coloring composition of the present invention. As for the shape of the resin-type dispersant having a carboxyl group, there are a straight-chain resin-type dispersant and a comb-shaped resin-type dispersant.

The basic dispersant (B) is preferably used in an amount of about 3 to 200% by mass, more preferably in an amount of about 3 to 100% by mass, based on the total amount of the coloring agent.

<Binder resin (C)>
The binder resin (C) can be classified into a binder resin (C1) containing a polymerizable unsaturated group and a binder resin (C2) containing no polymerizable unsaturated group. Among these, it is preferable to contain a photosensitive binder resin (C1) from the viewpoint of adhesion, pattern shape, and solvent resistance. From the standpoint of developability, the binder resin (C) preferably has an alkali-soluble group. The alkali-soluble group includes, for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, a phenolic hydroxyl group, etc. Among these, a carboxyl group is preferred.
Moreover, the binder resin (C) can contain a thermosetting group such as an epoxy group or an oxetanyl group.

(Binder Resin (C1) Containing Polymerizable Unsaturated Group)
Binder resins (C1) containing polymerizable unsaturated groups include, for example, acrylic resins having acidic groups, α-olefin/(anhydride) maleic acid copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth ) acrylic acid copolymers or isobutylene/(anhydrous) maleic acid copolymers. Among these, acrylic resins having acidic groups and styrene/styrenesulfonic acid copolymers are preferred.

(Binder Resin (C1) Containing Polymerizable Unsaturated Group)
The binder resin (C1) containing a polymerizable unsaturated group is a binder resin having a polymerizable unsaturated group. The binder resin (C1) containing a polymerizable unsaturated group is preferably, for example, a resin synthesized by the method (i) or (ii) shown below.

[Method (i)]
Method (i), for example, first synthesizes a polymer of an epoxy group-containing monomer and other monomers. Next, a monomer containing a monocarboxyl group is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain a binder resin (C1) containing a polymerizable unsaturated group. method.

Epoxy group-containing monomers include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4- Epoxycyclohexyl (meth)acrylates can be mentioned. Among these, glycidyl (meth)acrylate is preferable from the viewpoint of reactivity.

Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t- Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate Acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethylene oxide (EO)-modified cresol acrylate, n-nonyl Phenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, EO-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, nonylphenol (Meth)acrylates such as PO-modified (meth)acrylates of
(Meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone (meth)acrylamide, or (meth)acrylamides such as acryloylmorpholine ;
styrene or styrenes such as α-methylstyrene;
vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate or vinyl propionate;
cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedi maleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl -N-substituted maleimides such as 6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine;
2-(meth)acryloyloxyethyl acid phosphate, a phosphate ester group-containing unit such as a compound obtained by reacting a hydroxyl group of a hydroxyl group-containing monomer described later with a phosphorylating agent such as phosphorus pentoxide or polyphosphoric acid mers, which can be used singly or in combination of two or more.

Monocarboxyl group-containing monomers are, for example, (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth)acrylic acid, alkoxyl, halogen, nitro, cyano-substituted and monocarboxylic acids such as monocarboxylic acids, which can be used singly or in combination of two or more.

Polybasic acid anhydrides include, for example, tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and can be used alone or in combination of two or more. In addition, if necessary, a tricarboxylic dianhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic anhydride can be used to hydrolyze the remaining anhydride groups.

As a method similar to method (i), for example, a polymer of a carboxyl group-containing monomer and other monomers is synthesized. Next, there is a method of adding an epoxy group-containing monomer to a part of the carboxyl groups of the polymer to obtain a binder resin (C1) containing a polymerizable unsaturated group.

[Method (ii)]
Method (ii) synthesizes polymers of, for example, hydroxyl group-containing monomers, monocarboxyl group-containing monomers, and other monomers. Next, a method of reacting the hydroxyl group of the polymer with the isocyanate group of the isocyanate group-containing monomer can be mentioned.

Hydroxyl group-containing monomers, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylates or hydroxyalkyl methacrylates such as cyclohexanedimethanol mono(meth)acrylate; In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to hydroxyalkyl (meth)acrylate, poly γ-valerolactone, poly ε-caprolactone, and/or poly Polyester mono(meth)acrylates to which 12-hydroxystearic acid or the like is added are also included. These can be used alone or in combination of two or more. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred because foreign substances are less likely to form in the coating. In terms of photosensitivity, glycerol mono(meth)acrylate is preferred.

Isocyanate group-containing monomers include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate, which may be used alone or in combination of two or more. Can be used together.

As the monocarboxyl group-containing monomer and other monomers, the monomers described above can be used.

The weight average molecular weight (Mw) of the binder resin (C) is preferably 2,000 to 40,000, more preferably 3,000 to 300,00, particularly preferably 5,000 to 25,000. Also, the value of Mw/Mn is preferably 10 or less.

The acid value of the binder resin (C) is preferably 40-200 mgKOH/g, more preferably 50-180 mgKOH/g.

The binder resin (C) can be used alone or in combination of two or more types, and from the viewpoint of developability, adhesion, pattern shape, and solvent resistance, two or more polymerizable resins having different weight average molecular weights (Mw) It preferably contains a binder resin (C1) containing an unsaturated group. Among them, a binder resin (C1-1) containing a polymerizable unsaturated group having a weight average molecular weight (Mw) of 12,000 or less and a polymerizable unsaturated group having a weight average molecular weight (Mw) of 18,000 or more It is preferable to use the binder resin (C1-2) together, and a photosensitive binder resin (C1-1) having a weight average molecular weight (Mw) of 5,000 to 10,000 and a weight average molecular weight (Mw) of 20, 000 to 25,000 photosensitive binder resin (C1-2) is more preferably used in combination.

A binder resin (C1-1) containing a polymerizable unsaturated group having a weight average molecular weight (Mw) of 12,000 or less and a binder resin containing a polymerizable unsaturated group having a weight average molecular weight (Mw) of 18,000 or more The mass ratio to (C1-2) is preferably 20:80 to 80:20, more preferably 30:70 to 70:30, from the viewpoints of developability, adhesion, pattern shape and solvent resistance.

The content of the binder resin (C) is preferably 20 to 400 parts by mass, more preferably 30 to 250 parts by mass, per 100 parts by mass of the colorant (A).

<Polymerizable Monomer (D)>
The photosensitive coloring composition of the present invention contains, as the polymerizable monomer (D), a polymerizable monomer (D1) containing a fluorene skeleton and having a glass transition temperature (Tg) of 200° C. or less. . Polymerizable monomers (D) are monomers (also referred to as monomers) and oligomers containing polymerizable unsaturated groups. Examples of polymerizable unsaturated groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, and (meth)acryloyloxy groups.

Commercially available polymerizable monomers (D1) containing a fluorene skeleton and having a glass transition temperature of 200° C. or less include OGSOL EA-0300 and GA-2800 manufactured by Osaka Gas Chemicals.

A cured film is prepared by reacting a polymerizable monomer (D1) containing a fluorene skeleton and having a glass transition temperature of 200° C. or less with a photopolymerization initiator, and the cured film is measured by differential scanning calorimetry. Specifically, it was measured by the method described in Example 2 of JP-A-2009-173646.

The polymerizable monomer (D1) containing a fluorene skeleton and having a glass transition temperature of 200° C. or lower is preferably a compound represented by the following general formulas (1) and (2).

General formula (1)

(In general formula (1), R1 and R3 each independently represent a hydrogen atom or a methyl group, R2 and R4 each independently represent an alkylene group, m and n each independently represent an integer of 1 to 10 represents.)

general formula (2)

(In general formula (2), R5 and R7 each independently represent a hydrogen atom or a methyl group, R6 and R8 each independently represent an alkylene group, x and y each independently represent an integer of 1 to 10 represents.)

Examples of the polymerizable monomer (D) in the present invention include monomers and oligomers that form transparent resins by curing with ultraviolet rays or heat. Examples include 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, trimethylolpropane tri(meth)acrylate, phenoxytetraethyleneglycol (meth)acrylate, phenoxyhexaethyleneglycol (meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate ) acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanurate EO-modified di(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate , pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, methylolated melamine (meth) acrylic acid ester, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate, and Methacrylic acid ester, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, etc. are included, but are not necessarily limited to these.

These commercially available products include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO- 303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, and Aronix M-303, M manufactured by Toagosei Co., Ltd. -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, Viscoat #310HP, #335HP, #700, #295 manufactured by Osaka Organic Co., Ltd. , #330, #360, #GPT, #400, #405, NK Ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and the like can be preferably used.

(Polymerizable compound having acid group)
The polymerizable monomer (D) in the invention may contain a polymerizable compound having an acid group. By using a polymerizable compound having an acid group, when the photosensitive coloring composition of the present invention is subjected to alkali development, the solubility of the formed coating film in an alkali developer can be increased, and the development speed can be improved or residue can be reduced. Examples of acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups.

Examples of the polymerizable compound having an acid group include, for example, poly(meth)acrylates containing free hydroxyl groups of polyhydric alcohol and (meth)acrylic acid, and esters of dicarboxylic acids; Esterified products with (meth)acrylates and the like can be mentioned. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. and free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic 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, 2-hydroxyethyl acrylate, 2- Monohydroxy monoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates, etc., but the effects of the present invention are limited to these. not to be

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

(Polymerizable compound having urethane bond)
The polymerizable monomer (D) in the invention may contain a polymerizable compound containing at least one ethylenically unsaturated bond and at least one urethane bond. By containing a polymerizable compound having a urethane bond, it is possible to suppress deposition of a coloring material when the formed coating film is heated, and to improve solvent resistance and adhesion to a substrate.

As the polymerizable compound having a 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 an alcohol with a polyfunctional isocyanate and further having a hydroxyl group (meth) ) polyfunctional urethane acrylates obtained by reacting acrylates, and the like.

(Meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri( meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate Examples include methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylates.

Polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate and the like.

These commercial products include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., Shin-Nakamura Chemical Co., Ltd. UA-160TM, manufactured by Osaka Organic Chemical Industry Co., Ltd., UV-4108F, UV-4117F, etc. can be preferably used.

The above-mentioned polymerizable monomer (D) can be used by mixing one type or two types with the polymerizable monomer (D1) at an arbitrary ratio, if necessary.

The blending amount of the polymerizable monomer (D) is preferably 1 to 50 parts by mass based on the total solid content of the photosensitive coloring composition (100 parts by mass). The ratio of polymerizable monomer (D1) to polymerizable monomer (D) is preferably 50:50 to 80:20, more preferably 80:20 to 90:10, most preferably 90:10 to 100:0. is.

[Photoinitiator (E)]
The photosensitive coloring composition of the present invention contains a photopolymerization initiator (E). By including the photopolymerization initiator (E), the photosensitive coloring composition can be cured by ultraviolet irradiation to form a cured film.

The photopolymerization initiator (E) is not particularly limited as long as it is a compound capable of initiating polymerization of the polymerizable monomer (C) by light, and known photopolymerization initiators can be used. For example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl )-1-butanone, or acetophenone compounds such as 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone;
2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s -triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloro methyl)-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 triazines such as 2,4-trichloromethyl-(4′-methoxystyryl)-6-triazine system compound;
1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)], or ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole oxime compounds such as 3-yl]-, 1-(O-acetyloxime);
Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide;
quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds;

Commercially available products include Omnirad 907, 369, 379EG manufactured by IGM Resins as acetophenone-based compounds, and Omnirad 819 and TPO manufactured by IGM Resins as acylphosphine-based compounds.
As the oxime compound (E1), IRGACURE OXE-01, 02, 03, 04 manufactured by BASF Japan, N-1919, 730, 831, 930 manufactured by ADEKA, and TRONLY TR-PBG- manufactured by Changzhou Tenryu New Materials Co., Ltd. 301, 304, 305, 309, 345, 346, 358, 3054, 3057, OMNIRAD 1312, 1314, 1316 manufactured by IGM Resins, SPI-02, 03, 04, 05, 06, 07 manufactured by Samyang Corporation, Daito Chemics DFI-020, 036, EOX-01, etc. manufactured by In addition, JP 2005-215378, JP 2011-105713, JP 2017-523465, JP 2007-210991, JP 2009-179619, JP 2010-037223, Also included are oxime compounds (E1) described in JP-A-2010-215575, JP-A-2011-020998, and WO 2015/036910.

Among these, the oxime compound (E1) is preferable from the viewpoint of reactivity and pattern formability.

A photoinitiator (E) can be used individually or in combination of 2 or more types.

From the viewpoint of adhesion and pattern shape, the content of the photopolymerization initiator (E) is 0 with respect to the total mass of the binder resin (C1) containing a polymerizable unsaturated group and the polymerizable monomer (D). .5 to 10% by weight is preferred, 1 to 5% by weight is more preferred, and 1 to 3% by weight is most preferred.

[Acidic dispersant (F)]
The photosensitive coloring composition of the present invention preferably contains an acidic dispersant (F) having an acidic group such as a carboxyl group.
[Comb-shaped resin-type dispersant having carboxyl group (F1)]
The comb-shaped resin-type dispersant (F1) having a carboxyl group can be produced by known methods such as those disclosed in WO2008/007776, JP-A-2008-029901, JP-A-2009-155406, and the like.
For example, a resin-type dispersant that is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride, or a hydroxyl group of a compound having a hydroxyl group and a tetracarboxylic dianhydride It is a resin-type dispersant that is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product with an acid anhydride group of a compound.

The acidic dispersant (F) is preferably used in an amount of about 3 to 200% by mass, more preferably in an amount of about 3 to 100% by mass, based on the total amount of the coloring agent.

[Sensitizer (G)]
The photosensitive coloring composition of the present invention can contain a sensitizer (G).

Sensitizers (G) include, for example, chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and 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, indolines derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphy Radin derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler-ketone derivatives , α-acyloxy ester, acyl oxide, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3′ or 4 ,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone and the like.

Among the sensitizers (G), thioxanthone derivatives, Michler-ketone derivatives and carbazole derivatives are preferred. Specific compounds are 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole and the like are preferred.

A sensitizer (G) can be used individually or in combination of 2 or more types.

The content of the sensitizer (G) is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator (E). When contained in an appropriate amount, photocurability and developability are improved.

[Thermosetting compound (H)]
The photosensitive coloring composition of the present invention can contain a thermosetting compound (H). As a result, the thermosetting compound (H) reacts in the heating step, increasing the crosslink density and improving the heat resistance.

The thermosetting compound (H) may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. Thermosetting compounds (H) include, for example, epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

(Epoxy compound (H1))
Epoxy compounds (H1) include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene , alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Polymerization of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'- benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, and the like.

Commercially available products include, for example, EPICOAT 807, 815, 825, 827, 828, 190P, 191P manufactured by Yuka Shell Epoxy Co., Ltd., TECHMORE VG3101L manufactured by Mitsui Chemicals, EPPN-201, 501H, 502H manufactured by Nippon Kayaku, EOCN-102S, 103S, 104S, 1020 Epikote 1004, 1256 manufactured by Japan Epoxy Resin Co., Ltd., JER1032H60, 157S65, 157S70, 152, 154, Celoxide 2021 manufactured by Daicel Chemical Industries, EHPE-3150, Denacol manufactured by Nagase ChemteX Corporation EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721, Nissan Chemical Industries TEPIC-L, H, S, etc. is mentioned.

The content of the epoxy compound (H1) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition.

(Oxetane compound (H2))
The oxetane compound (H2) is a known compound having an oxetane group. Oxetane compounds include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher oxetane compounds.

Monofunctional oxetane compounds include, for example, (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxy silyl)propoxy]methyl}oxetane and the like.

Examples of commercially available products include OXE-10 and 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101 and 212 manufactured by Toagosei Co., Ltd., and the like.

Bifunctional oxetane compounds include, for example, 4,4′-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3 -ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)- 5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol-bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3 -ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3- ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanyl) methyl) ether and the like.

Commercially available products include, for example, OXBP and OXTP manufactured by Ube Industries, and OXT-121 and 221 manufactured by Toagosei.

Trifunctional or higher oxetane compounds include, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3 -oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl- 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups ( For example, oxetane-modified phenolic novolak resins described in Japanese Patent No. 3783462) and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30 can be mentioned.

The content of the oxetane compound (H2) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, based on 100% by mass of the nonvolatile matter of the photosensitive coloring composition.

A melamine compound is a compound having a melamine ring structure. The melamine compound is preferably a methylol-type or ether-type compound, and more preferably a melamine compound having an average number of methylol groups and/or ether groups of 5.0 or more per melamine ring. Having an appropriate number of methylol groups and ether groups makes it easy to obtain just the right amount of heat resistance.

Commercially available products include, for example, Sanwa Chemical Co., Ltd. Nicarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX- 417, MX-410, and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 manufactured by Nippon Cytec Industries.

Among these, Nicarac MW-30HM, MW-390, MW-100LM and MX manufactured by Sanwa Chemical Co., Ltd., having an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more. -750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45, Cymel 232, 235, 236, 238, 300, 301 manufactured by Nihon Cytec Industries, 303, 350 and the like are preferable in terms of increasing the crosslink density.

A thermosetting compound (H) can be used individually or in combination of 2 or more types.

[Curing agent (curing accelerator)]
The photosensitive coloring composition of the present invention can be used in combination with a curing agent (curing accelerator) to assist curing of the thermosetting compound (H). Curing agents include, for example, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like. Curing agents include, for example, amine compounds (eg, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds and their salts (e.g., imidazole, 2 -methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4 -methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino- S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.).

Curing agents can be used alone or in combination of two or more.

The content of the curing agent is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound (H).

[Thiol-based chain transfer agent (I)]
The photosensitive coloring composition of the present invention can contain a thiol chain transfer agent (I). The thiol-based chain transfer agent (I), when used in combination with the photopolymerization initiator (E), generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen during radical polymerization after light irradiation, and increases the photosensitivity of the photosensitive coloring composition. improves.

The thiol-based chain transfer agent (I) is preferably a polyfunctional thiol having two or more thiol groups (SH groups). The thiol-based chain transfer agent more preferably has 4 or more SH groups. As the number of functional groups increases, photocuring becomes easier from the surface to the deepest part of the film.

Polyfunctional thiols are, for example, hexanedithiol, decanedithiol, 1,4-butanedi-rubisthiopropionate, 1,4-butanedi-rubisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. , trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercapto tris(2-hydroxyethyl) isocyanurate propionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto- s-triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate and the like.

The thiol-based chain transfer agent (I) can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent (I) is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on 100% by mass of the nonvolatile matter of the photosensitive coloring composition. When contained in an appropriate amount, the photosensitivity is improved and wrinkles are less likely to occur on the pattern surface.

[Polymerization inhibitor (J)]
The photosensitive coloring composition of the present invention can contain a polymerization inhibitor (J).

Polymerization inhibitor (J) is, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol , 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-t-butylcatechol, 3-t-butylcatechol , 4-t-butylcatechol, 3,5-di-t-butylcatechol and other alkylcatechol compounds, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2 alkylresorcinol compounds such as -propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; Alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine phosphine compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol and phloroglucine;

The content of the polymerization inhibitor (J) is preferably 0.01 to 0.4% by mass based on 100% by mass of non-volatile matter in the photosensitive coloring composition.

[Ultraviolet absorber (K)]
The photosensitive coloring composition of the present invention can contain an ultraviolet absorber (K).

The ultraviolet absorber (K) is an organic compound having an ultraviolet absorption function, and includes benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylate-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds. compounds and the like.

Benzotriazole compounds include, for example, 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3 ,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2′- Hydroxy-5′-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1- dimethylethyl)-4-hydroxy, a mixture of 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, methyl 3-(3-(2H -benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol-2-yl)-4-(1,1,3, 3-tetramethylbutyl)phenol, 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H- benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5-di-t-amyl -2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy- 5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl ) phenyl]propionate.

Commercially available products are, for example, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF Japan, and Adekastab LA-29, LA-31RG, LA manufactured by ADEKA. -32, LA-36, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

Triazine compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4, 6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxy Reaction product of phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidate, 2,4-bis'2-hydroxy-4 -butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-( hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6- and tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Commercially available products include, for example, KEMISORB102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan, Adekastab LA-46, LA-F70 manufactured by ADEKA, and CYASORB UV- manufactured by Sun Chemical Co., Ltd. 1164 and the like.

Benzophenone compounds include, for example, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 5-sulfonic acid-3, water temperature, 2-hydroxy-4-n-octo xybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxy benzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like.

Commercially available products include, for example, KEMISORB10, 11, 11S, 12, 111 manufactured by Chemipro Chemicals, SEESORB101, 107 manufactured by Shipro Chemicals, Adekastab 1413 manufactured by ADEKA, and UV-12 manufactured by Sun Chemical.

Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like.

The content of the ultraviolet absorber (K) is preferably 5 to 70% by weight based on the total 100% by weight of the photopolymerization initiator (E) and the ultraviolet absorber (K).

[Antioxidant (L)]
The photosensitive coloring composition of the present invention can contain an antioxidant (L). The antioxidant (L) is a photopolymerization initiator (E) and a thermosetting compound (H) contained in the photosensitive coloring composition, which prevents yellowing due to oxidation during the thermal process during thermal curing and ITO annealing. prevent. In particular, when the colorant (A) concentration of the photosensitive coloring composition is high, the content of the polymerizable compound (C) is relatively decreased, so the amount of the photopolymerization initiator (E) is increased, and the thermosetting compound If (H) is added, the cured film tends to turn yellow. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented.

Antioxidants (L) include, for example, hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present invention, the antioxidant is preferably a compound containing no halogen atoms.

Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

Hindered phenol antioxidants include, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H ,3H,5H)-trione, 1,1,3-tris-(2′-methyl-4′-hydroxy-5′-t-butylphenyl)-butane, 4,4′-butylidene-bis-(2- t-butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearylpropionate, pentaerythritol tetrakis [3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8 , 10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3 ,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2′ -methylenebis(6-t-butyl-4-ethylphenol), 2,2′-thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis (dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[ 3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanedi-rubis[3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2'-thio- Bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2′-isobutylidene-bis- (4, 6-dimethyl-phenol), 2,2′-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, etc. is mentioned.

Commercially available products include, for example, ADEKA's Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330, and Chemipro's KEMINOX 101, 179, 76, 9425. , IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by BASF Japan, Cyanox CY-1790, CY-2777 manufactured by Sun Chemical Co., etc. mentioned.

Hindered amine antioxidants include, for example, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6 -tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6 -tetramethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate , 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensates of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine , Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl ) imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3, Ester of 5,5-trimethylhexanoic acid, 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, bis(2,2,6,6-tetramethyl-1-(octyloxy)decanedioate -4-piperidinyl) ester, the reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyliperidyl)[[3,5-bis(1, 1 dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, poly[[6-morpholino-s-triazine-2,4 -diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2, 2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, 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 etc.

Commercially available products are, for example, ADEKA's ADEKA STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87 , LA-402F, LA-502XP, KAMISTAB 29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin 111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan, Cyasorb UV-3346 manufactured by Sun Chemical Co., Ltd. , UV-3529, UV-3853 and the like.

Phosphorus antioxidants include, for example, di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, 2,2′-methylenebis(4,6 -di-t-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15alkyl)-4,4' -Isopropylidenediphenyldiphosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylisodecylphosphite, tris(isodecyl)phosphite, triphenylphosphite, tetrakis(2,4-di-t-butylphenyl)- 4,4-biphenyldiphosphonate, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4 '-isopropylidenediphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite Phyto, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4 -di-t-butyl-6-methylphenyl) and the like.

Commercial products include, for example, Adekastab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA, IRGAFOS168 manufactured by BASF Japan, and HostanoxP manufactured by Clariant Chemicals. -EPQ and the like.

Sulfur antioxidants include, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3′- ditridecyl thiobispropionate, 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 and the like.

Commercially available products include, for example, ADEKA STAB AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by Chemipro Kasei.

The antioxidant (L) can be used alone or in combination of two or more.

The content of the antioxidant (L) is preferably 0.5 to 5.0% by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When contained in an appropriate amount, transmittance, spectral characteristics, and sensitivity are improved.

[Leveling agent (M)]
The photosensitive coloring composition of the present invention can contain a leveling agent (M). This further improves the wettability and dryability of the substrate during coating. Examples of the leveling agent (M) include silicon surfactants, fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants and the like.

Silicon-based surfactants include, for example, linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains or terminals.

Commercially available products are, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377 manufactured by BYK Chemie, 378, 3455, UV3510, 3570, Toray Dow Corning FZ-7002, 2110, 2122, 2123, 2191, 5609, Shin-Etsu Chemical Co., Ltd. X-22-4952, X-22-4272, X- 22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341 and the like.

Fluorosurfactants include, for example, surfactants or leveling agents having fluorocarbon chains.

Commercially available products are, for example, Surflon S-242, 243, 420, 611, 651, 386 manufactured by AGC Seimi Chemical Co., Ltd., and Megafac F-253, 477, 551, 552, 555, 558, 560, 570 manufactured by DIC Corporation. , 575, 576, R-40-LM, R-41, RS-72-K, DS-21, Sumitomo 3M FC-4430, 4432, Mitsubishi Materials Electronic Chemicals EF-PP31N09, EF-PP33G1 , EF-PP32C1, and Ftergent 602A manufactured by Neos.

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyl Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan mono Laurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxytetraoleic acid Ethylene sorbitol, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamides, alkylimidazolines, and the like.

Commercially available products are, for example, Kao Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430 , 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90 , B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Rhodol SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V , SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60 (K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, Adeka Pluronic (registered trademark) L-23, 31 manufactured by ADEKA, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, Kyoeisha Chemical Co., Ltd. (meth)acrylic acid-based (co)polymer Polyflow-No. 75, No. 90, No. 95 and the like.

Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

Commercially available products include, for example, Acetamine 24, Kotamine 24P, 60W, 86P conch manufactured by Kao Corporation.

Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenylether disulfonates, and monoethanol lauryl sulfate. amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.

Commercially available products include, for example, Futergent 100 and 150 manufactured by Neos, Adeka Hope YES-25, Adekacol TS-230E, PS-440E and EC-8600 manufactured by ADEKA.

Amphoteric surfactants include, for example, lauramidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, alkylbetaines such as alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

Commercially available products include Amphithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N manufactured by Kao Corporation.

A leveling agent (M) can be used individually or in combination of 2 or more types.

The content of the leveling agent (M) is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on 100% by mass of non-volatile matter in the photosensitive coloring composition. Within this range, the balance between applicability and adhesion of the photosensitive coloring composition is further improved.

[Storage stabilizer (N)]
The photosensitive coloring composition of the present invention can contain a storage stabilizer (N). This stabilizes the viscosity of the photosensitive coloring composition over time. Storage stabilizers (N) include, for example, benzyltrimethyl chloride, quaternary ammonium chloride such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenyl and the like. organic phosphines, phosphites, and the like.

The content of the storage stabilizer (N) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant (A).

[Adhesion improver (O)]
The photosensitive coloring composition of the present invention can contain an adhesion improver (O). This improves the adhesion between the cured film and the substrate. In addition, it becomes easier to form a narrow pattern by photolithography.

Adhesion improvers (O) include, for example, silane coupling agents. Examples of silane coupling agents include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, (Meth)acrylsilanes such as 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxysilanes, N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3- dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, aminosilanes such as hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyl mercaptos such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureides such as 3-ureidopropyltriethoxysilane; Examples include silane coupling agents such as sulfides and isocyanates such as 3-isocyanatopropyltriethoxysilane.

Adhesion improvers (O) can be used alone or in combination of two or more.

The content of the adhesion improver (O) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the colorant (A).

[Organic solvent (P)]
The photosensitive composition of the invention can contain an organic solvent (P).

Organic solvent (P) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol Diacetate, 1,4-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-methoxy Butyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N -methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol 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 alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate , propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like. Among these, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and the like are preferred from the viewpoint of pigment dispersibility and alkali-soluble resin solubility. Alcohols such as glycol acetates, benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.

The organic solvent (P) can be used alone or in combination of two or more.

[Method for producing a photosensitive coloring composition]
The photosensitive coloring composition of the present invention includes, for example, a coloring agent (A), a binder resin (B), a polymerizable compound (C) and a photopolymerization initiator (E), a dispersing resin (F), an organic solvent (P) A dispersion is produced by performing a dispersion treatment by adding, etc. After that, the polymerizable compound (C) and the photopolymerization initiator (D) are added to the dispersion and mixed to produce the dispersion. The timing of blending each material is arbitrary. Moreover, a dispersion|distribution process can also be performed in multiple times.

Examples of the dispersing machine for performing the dispersing treatment include a two-roll mill, three-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, and attritor.

The average dispersed particle size (secondary particle size) of the colorant (A) in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. If the particle size is appropriate, a photosensitive coloring composition with high dispersion stability can be easily obtained.

The method for measuring the average dispersed particle size (secondary particle size) is, for example, using a Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd., which employs the dynamic light scattering method (FFT power spectrum method), and the particle permeability is measured by the absorption mode. The particle shape is assumed to be non-spherical, and the D50 particle diameter is defined as the average diameter. It is preferable to use the organic solvent used for dispersion as the diluent solvent for the measurement, and to measure the ultrasonically treated sample immediately after the sample preparation, because it is easy to obtain results with little variation.

The photosensitive coloring composition is separated from 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 It is preferable to remove mixed dust. The photosensitive coloring composition of the present invention preferably contains substantially no particles of 0.5 μm or more, more preferably no particles of 0.3 μm or less.

<Color filter>
The color filter of the present invention comprises a substrate and filter segments formed from the photosensitive coloring composition of the present invention. The color filter segment preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of coloring agent (A) used. Also, the color filter may have a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment instead of or in addition to the color filter segment.
Substrates include transparent substrates and reflective substrates. Examples of transparent substrates include glass substrates. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[Manufacturing method of color filter]
The method for manufacturing a color filter is not particularly limited. For example, a step (1) of applying a photosensitive coloring composition on a substrate to form a layer of the composition, and a step of patternwise exposing the layer through a mask. (2), the step (3) of forming a patterned cured film by developing the unexposed portion with alkali, and the step (4) of heat-treating (post-baking) the pattern.

A method for manufacturing a color filter will be described in detail below.
(Step (1))
In step (1) of forming a layer of the composition, the photosensitive coloring composition is applied onto the substrate by a method such as spin coating, roll coating, slit coating, casting coating, or inkjet coating, If necessary, it is dried (pre-baked) at a temperature of 50 to 120° C. for 10 to 120 seconds using an oven, hot plate, or the like.
Examples of the substrate include a glass substrate and a silicon substrate. The silicon substrate may have, for example, an imaging element such as a CCD or CMOS formed on its surface. In addition, if necessary, an undercoat layer may be provided on the substrate for improving adhesion with the upper layer, preventing diffusion of substances, and flattening the surface of the substrate.
The thickness of the layer after drying is preferably 0.05 to 10.0 μm, more preferably 0.3 to 5 μm.

(Step (2))
In the exposure step, the layer obtained in step (1) is exposed to a specific pattern through a mask using an exposure device such as a stepper. A cured film is thus obtained.
Radiation used for exposure includes, for example, ultraviolet rays such as g-line, h-line and i-line.

(Step (3))
The cured film obtained in step (2) is subjected to alkali development treatment, whereby the layer of the composition in the unexposed portions is eluted in an alkaline aqueous solution, leaving only the cured portions to obtain a patterned cured film.
Developers include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include alkaline compounds such as pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene.
The concentration of the developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
The pH of the alkaline developer is preferably 11-13, more preferably 11.5-12.5. When used at an appropriate pH, pattern roughness and peeling can be suppressed, and the residual film rate after development can be improved.

The developing method includes, for example, a dipping method, a spraying method, a paddling method and the like. The developing temperature is preferably 15 to 40°C. In addition, it is preferable to wash with pure water after alkali development.

(Step (4))
In the heat treatment (post-baking), the patterned cured film obtained in step (3) is sufficiently cured by heating. The heating temperature for post-baking is preferably 100 to 300.degree. C., more preferably 150 to 250.degree. The heating time is preferably about 2 minutes to 1 hour, more preferably about 3 minutes to 30 minutes.

<Image display device>
An image display device of the present invention includes the color filter of the present invention.
The form used for the image display device is not particularly limited as long as it functions as an image display device. For example, there is a configuration described in "Next Generation Liquid Crystal Display Technology" (written by Tatsuo Uchida, published by Industrial Research Institute, 1994).
For the definition of the image display device and the details of each image display device, see, for example, "Electronic Display Device (written by Akio Sasaki, Industrial Research Institute, 1990)", "Display Device (written by Junsho Ibuki, Sangyo Tosho Co., Ltd., published in 1989).

FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 having a color filter of the present invention. The device 10 shown in FIG. 1 comprises a pair of transparent substrates 11 and 21 spaced and opposed to each other, with a liquid crystal LC sealed between them.

A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of ITO, for example, is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13 . A polarizing plate 15 is formed on the outer surface of the transparent substrate 11 .

On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21 . The red, green and blue filter segments that make up color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed as necessary to cover the color filters 22, and a transparent electrode layer 23 made of, for example, ITO is formed thereon. is provided.

A polarizing plate 25 is formed on the outer surface of the transparent substrate 21 . A backlight unit 30 is provided below the polarizing plate 15 .

<Solid-state image sensor>
A solid-state imaging device of the present invention includes the color filter of the present invention.
The form used for the solid-state imaging device is not particularly limited. It has an electrode, has a light-shielding film on the photodiode and the transfer electrode with only the light-receiving portion of the photodiode opened, and is made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode. It has a device protective film and has a color filter on the device protective film. Furthermore, a configuration having a condensing means (for example, a microlens or the like; the same shall apply hereinafter) on the device protective film and below the color filter (on the side closer to the base material), a configuration having a condensing means on the color filter, etc. may be Moreover, the color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned, for example, in a grid pattern by partition walls. The partition wall in this case preferably has a low refractive index for each color pixel.
An imaging device equipped with the solid-state imaging device of the present invention can be used not only for digital cameras and electronic devices having imaging functions (mobile phones, smart phones, etc.), but also for vehicle-mounted cameras and surveillance cameras.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these. In addition, "part" is "mass part" and "%" is "mass%".

Prior to Examples, each measuring method will be described.
The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH/g) and amine value (mgKOH/g) of the resin are as follows.

(Average molecular weight of binder resin and dispersion resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the binder resin and dispersion resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the apparatus, two separation columns were connected in series, and "TSK-GEL SUPER HZM-N" was used as both packing materials, and the oven temperature was 40 ° C. , using a tetrahydrofuran (THF) solution as an eluent and measuring at a flow rate of 0.35 ml/min. The sample was dissolved in a solvent consisting of 1% by weight of the above eluent and injected at 20 microliters. A molecular weight is a polystyrene conversion value.

(Acid value of binder resin and dispersion resin)
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the binder resin and dispersion resin solution and stirred to dissolve uniformly. 555” manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mgKOH/g). Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the concentration of the nonvolatile content of the resin solution.

(Amine value of dispersion resin)
The amine value of the dispersing resin is a value obtained by converting the total amine value (mgKOH/g) measured according to the method of ASTM D 2074 into the non-volatile content.

<Production of colorant (A)>
(Micronized green pigment (A-1))
C. I. 100 parts of Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 6 hours. This kneaded product is put into 3000 parts of hot water, stirred for 1 hour while heating to 70 ° C. to make a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and dried at 80 ° C. for a day and night to obtain a fine slurry. A converted green pigment (A-1) was obtained.

(Micronized yellow pigment (A-2))
C. I. Pigment Yellow 150 (100 parts), sodium chloride (700 parts) and diethylene glycol (180 parts) were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. This mixture is poured into 2,000 parts of warm water, stirred for 1 hour while heating to 80°C to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, dried at 80°C for a day and night, and finely ground. A converted yellow pigment (A-2) was obtained.

<Production of basic dispersant (B)>
(Basic dispersant (B-1) solution)
250 parts by mass of tetrahydrofuran (THF) and 5.81 parts by mass of dimethylketenemethyltrimethylsilyl acetal as an initiator were placed in a 500 mL round bottom four-necked separable flask equipped with a condenser, dropping funnel, nitrogen inlet, mechanical stirrer, and digital thermometer. was added through the dropping funnel, and the mixture was sufficiently purged with nitrogen. 0.5 parts by mass of a 1 mol/L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 19.7 parts by mass of 2-hydroxyethyl methacrylate as a block monomer having solvent affinity. , 7.5 parts by mass of 2-ethylhexyl methacrylate, 12.9 parts by mass of n-butyl methacrylate, 10.7 parts by mass of benzyl methacrylate, and 30.9 parts by mass of methyl methacrylate were added for 60 minutes using a dropping funnel. dripped. The temperature was kept below 40° C. by cooling the reaction flask with an ice bath. After 1 hour, 18.3 parts by mass of dimethylaminopropyl methacrylamide, which is a monomer for colorant adsorption functional block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to terminate the reaction. The resulting block copolymer THF solution was reprecipitated in hexane, filtered and vacuum dried for purification.
Subsequently, 15.0 parts by mass of the obtained block copolymer was dissolved in 35 parts by mass of propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMAc) in a 100 mL round-bottomed flask, and phenylphosphinic acid, which is a salt-forming component, was dissolved. 1.1 parts by mass (0.5 molar equivalents relative to dimethylaminopropyl methacrylamide) was added, stirred at a reaction temperature of 30 ° C. for 20 hours, adjusted by adding PGMAc, and a basic dispersant having a nonvolatile content of 30% ( B-1) A solution was obtained.

<Production of binder resin (C)>
Binder resins (C1-1-1) to (C1-1-4), (C1-3), (C1- 2-1) to (C1-2-4) and (C2-1) to (C2-2) were synthesized, and PGMAc was added to adjust the non-volatile content to 20%.

The synthesis method and production method were performed according to the description of JP-A-2020-060631.

The terms shown in Tables 1-2 are as follows.
GMA+AA: Polymerizable unsaturated group-containing monomer obtained by reacting the epoxy group of glycidyl methacrylate with acrylic acid GMA+AA+TPHA: Fatty acid anhydride-modified polymerizable unsaturated monomer obtained by subjecting the hydroxyl group of GMA+AA to the esterification reaction of tetrahydrophthalic anhydride Group-containing monomers GMA+MAA: polymerizable unsaturated group-containing monomers obtained by reacting the epoxy group of glycidyl methacrylate with methacrylic acid

<Production of acidic dispersant (F)>
(Acidic dispersant (F-1) solution)
10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate and 50 parts of PGMAc were introduced into a reaction vessel equipped with a gas inlet tube, a temperature control, a condenser and a stirrer, and the atmosphere was purged with nitrogen gas. The inside of the reaction vessel was heated to 50° C. with stirring, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90° C., and the mixture was reacted for 7 hours while adding a solution of 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of PGMAc. It was confirmed by measuring the non-volatile content that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 100° C. for 7 hours. . After confirming that 98% or more of the acid anhydride is half-esterified by acid value measurement, the reaction is terminated, and PGMAc is added to dilute the nonvolatile matter to 30%, and the acid value is 70 mgKOH / g, weight average An acidic dispersant (F-1) solution with a molecular weight of 8,500 was obtained.

<Production of dispersion>
(Dispersion 1)
After stirring and mixing the following raw materials uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), the pore size It was filtered through a 1.0 μm filter to prepare Dispersion 1. Organic solvent (P-1) is PGMAc.
Finely divided green pigment (A-1): 9.7 parts Finely divided yellow pigment (A-2): 4.4 parts Basic dispersant (B-1) solution: 19.5 parts Organic solvent (P- 1): 66.4 parts

Dispersions 1 to 5 were obtained by changing the compounding species and amount so that the composition ratios shown in Table 3 were obtained.

<Production of photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition 1)
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition 1.
Dispersion 1: 56.5 parts Polymerizable unsaturated group-containing binder resin (C1-1-3) solution: 11.5 parts Polymerizable unsaturated group-containing binder resin (C1-2-2) solution: 8.5 parts Polymerizable compound (D1-1): 2.5 parts Photoinitiator (E1-1): 0.15 parts Leveling agent (M): 1.0 parts Organic solvent (P): 19.85 parts

The types and amounts were changed so that the composition ratios shown in Tables 4 to 9 were obtained, and photosensitive coloring compositions 1 to 38 were obtained.

[Polymerizable compound (C)]
(D1, a compound represented by the general formula (1) having a Tg of 200° C. or less)
・ D1-1: OGSOL EA-0300 (manufactured by Osaka Gas Chemicals, Tg 17 ° C.)
・ D1-2: OGSOL GA-2800 (manufactured by Osaka Gas Chemicals Co., Ltd., Tg 7 ° C.)
(D2, not a compound represented by the general formula (1), or having a Tg of more than 200°C)
・ D2-1: Aronix M-402 (manufactured by Toagosei Co., Ltd., trimethylolpropane ethylene oxide-modified triacrylate)
・ D2-2: OGSOL EA-0200 (manufactured by Osaka Gas Chemicals, Tg 211 ° C.)

[Photoinitiator (E)]
(Oxime compound)
・ E1-1: ADEKA CRUISE NCI-831 (manufactured by ADEKA)
・ E1-2: Irgacure OXE04 (manufactured by BASF Japan)
(acetophenone compound)
・ E2: Irgacure 907 (manufactured by BASF Japan)

[Leveling agent (M)]
One part each of BYK-330 (manufactured by BYK-Chemie) and Megafac F-551 (manufactured by DIC) was mixed and dissolved in 98 parts of PGMAc to prepare a mixed solution as a leveling agent (M).

[Organic solvent (P)]
80 parts of PGMAc, 10 parts of cyclohexanone and 10 parts of ethyl 3-ethoxypropionate were mixed to prepare an organic solvent (P).

<Evaluation of photosensitive coloring composition>
The photosensitive coloring compositions 1 to 38 were evaluated for developability, adhesion and pattern shape by the following methods. Table 10 shows the evaluation results.

[Developability]
The obtained photosensitive coloring compositions 1 to 38 were applied to a glass substrate (Eagle 2000 manufactured by Corning Inc.) having a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm using a spin coater so that the dry film thickness was 2.0 μm. It was coated and dried on a hot plate at 70°C for 1 minute. Then, using an ultra-high pressure mercury lamp, the film was exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width at an illumination intensity of 30 mW/cm ² and 50 mJ/cm ² . Furthermore, after cooling this substrate to room temperature, it was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23° C. at two levels of development time (40 seconds, 70 seconds), and deionized water. and air-dried to form a striped pattern on the substrate. The pattern was observed with an optical microscope, and the presence or absence of development residues in unexposed areas and chipping was evaluated. The evaluation criteria are as follows, and 3 or more is practical.
5: At the development time of 70 seconds, there was no development residue in the unexposed area, and there was no missing pattern.
4: At the development time of 70 seconds, slight development residue or slight pattern missing occurred in the unexposed area.
3: At the development time of 70 seconds, development residue occurred or pattern missing occurred in the unexposed area.
2: At the development time of 40 seconds, a large amount of development residue occurred in the unexposed area, or a large amount of missing pattern occurred.
1: Pattern missing occurred at development time of 40 seconds.

[Adhesion]
The obtained photosensitive coloring compositions 1 to 38 are spin-coated onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) having a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm. and dried on a hot plate at 70°C for 1 minute. Then, after cooling the substrate to room temperature, it was exposed to light at an illumination intensity of 30 mW/cm ² and 50 mJ/cm ² using a high-pressure mercury lamp through a photomask having a stripe pattern with a width of 5 μm. After that, the substrate was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23° C., washed with deionized water, air-dried, and heated in a clean oven at 230° C. for 30 minutes for evaluation. obtained a substrate for The spray development was carried out for the shortest time in which a pattern can be formed without leaving any development residue on the film with each photosensitive coloring composition, and this was taken as the appropriate development time.
A thin line pattern having a width of 5 to 25 μm among the patterns of the substrate for evaluation was observed with an optical microscope to confirm the minimum line width of the remaining thin line pattern. The evaluation criteria are as follows, and 3 or more is practical.
5: Fine lines of 10 μm or less remain.
4: Fine lines of 15 μm or less remain.
3: Fine lines of 20 μm or less remain.
2: Fine lines of 25 μm or less remain.
1: Fine lines do not remain.

[Pattern shape (cross-sectional shape evaluation)]
The pattern shape of the substrate prepared for adhesion evaluation was confirmed using a scanning electron microscope ("S-3000H" manufactured by Hitachi High-Tech Co., Ltd.). For the evaluation, a cross-sectional SEM image of a striped pattern with a width of 100 μm was captured, and the cross-sectional shape was evaluated by measuring the taper angle between the substrate and the end of the cross-section of the pattern. The evaluation criteria are as follows, and 3 or more is regarded as practical.
5: Taper angle of 30 degrees or more and less than 50 degrees 4: Taper angle of 50 degrees or more and less than 60 degrees 3: Taper angle of less than 30 degrees or 60 degrees or more and less than 70 degrees 2: Taper angle of 70 degrees or more and less than 90 degrees 1: Taper angle of 90 degrees that's all

10 liquid crystal display device 11 transparent substrate 12 TFT array 13 transparent electrode layer 14 alignment layer 15 polarizing plate 21 transparent substrate 22 color filter 23 transparent electrode layer 24 alignment layer 25 polarizing plate 30 backlight unit 31 white LED light source LC liquid crystal

Claims (11)

A photosensitive coloring composition comprising a coloring agent (A), a basic dispersant (B), a binder resin (C), a polymerizable monomer (D), and a photopolymerization initiator (E),
The binder resin (C) contains a binder resin (C1) containing a polymerizable unsaturated group,
A photosensitive coloring composition, wherein the polymerizable monomer (D) contains a polymerizable monomer (D1) containing a fluorene skeleton and having a glass transition temperature of 200° C. or lower. The photosensitive coloring composition according to claim 1, wherein the content of the polymerizable monomer (D1) is 50% by mass or more in 100% by mass of the polymerizable monomer (D). The content of the photopolymerization initiator (E) is 0.5 to 10% by mass with respect to the total mass of the binder resin (C1) containing the polymerizable unsaturated group and the polymerizable monomer (D). A photosensitive coloring composition according to claim 1 or 2. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the binder resin containing a polymerizable unsaturated group (C1) comprises at least two binder resins having different weight average molecular weights. The binder resin (C1) containing a polymerizable unsaturated group is a binder resin (C1-1) containing a polymerizable unsaturated group having a weight average molecular weight of 12000 or less and a polymerizable unsaturated group having a weight average molecular weight of 18000 or more. The photosensitive coloring composition according to any one of claims 1 to 4, comprising a binder resin (C1-2) containing a group. Mass of the binder resin (C1-1) containing a polymerizable unsaturated group having a weight average molecular weight of 12000 or less and the binder resin (C1-2) containing a polymerizable unsaturated group having a weight average molecular weight of 18000 or more A photosensitive coloring composition according to claim 5, wherein the ratio is from 20:80 to 80:20. The photopolymerization initiator (E) comprises an oxime compound (E1), the photosensitive coloring composition according to any one of claims 1 to 6. Furthermore, the photosensitive coloring composition according to any one of claims 1 to 7, comprising an acidic dispersant (F). A color filter having a substrate and a filter segment formed using the photosensitive coloring composition according to any one of claims 1 to 8. An image display device comprising the color filter according to claim 9 . A solid-state imaging device comprising the color filter according to claim 9 .

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