JP2022172508A - Yellow colorant, coloring composition, color filter, and sensor including the same, and method for producing yellow colorant - Google Patents

Abstract

To provide a yellow colorant that strikes a balance between high tinting power and high transmittance and also provide a coloring composition that shows excellent stability when blended with another coloring composition, and a color filter and a sensor including the same.SOLUTION: A yellow colorant (A) contains a pigment represented by the following chemical formula (1). The yellow colorant (A) is boiled with distilled water and then filtered, resulting in a filtrate with a pH of 6.0-7.0.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a yellow coloring agent, a coloring composition, a color filter, a sensor using the same, and a method for producing a yellow coloring agent.

In recent years, with the spread of digital cameras and camera-equipped mobile phones, the demand for image sensors such as C-MOS (Complementary Metal Oxide Semiconductor) and CCD (Charge Coupled Device) has grown significantly. ing. These image sensors generally perform color separation by arranging color filters each having filter segments of additive primary colors of B (blue), G (green), and R (red) on the light receiving elements. is.

Color filters for image sensors are required to have thinner films, improved color resolution, and improved color reproducibility. Needed. In particular, in order to increase the coloring of the coloring composition, the concentration of the coloring agent is increased, the coloring agent having a high coloring power is used, and the like.

Conventionally, in the production of green and red filter segments, C.I. I. Colorants including Pigment Yellow 139 have been used (US Pat. However, conventional C.I. I. A coloring agent containing Pigment Yellow 139 has a problem that when the coloring composition has a high concentration, the viscosity increases when mixed with another coloring composition. In addition, there is a problem that the coloring power is not always satisfactory in response to the recent strong demand for thinner films, and that an attempt to increase the coloring power results in a decrease in transmittance.

JP 2014-178676 JP 2015-081932 JP 2017-083578

An object of the present invention is to provide a yellow colorant that achieves both high tinting strength and high transmittance. Another object of the present invention is to provide a coloring composition having good stability when mixed with another coloring composition, and a color filter and sensor using the same.

The inventors of the present invention have made intensive studies to solve the above problems, and found that a yellow coloring agent (A) containing a pigment represented by the following chemical formula (1), wherein the yellow coloring agent (A) After boiling with distilled water, the filtrate when filtered is a yellow coloring agent (A) characterized by having a pH of 6.0 to 7.0. A coloring composition containing a yellow coloring agent (A), a binder resin, and a solvent was found to have good stability when mixed with another coloring composition, and the invention was made based on this finding. be.

chemical formula (1)

That is, the present invention provides a yellow coloring agent (A) containing a pigment represented by the following chemical formula (1), wherein the yellow coloring agent (A) is boiled in distilled water and then filtered, and the filtrate has a pH of = 6.0 to 7.0 for a yellow colorant (A).

chemical formula (1)

Further, in the present invention, the content ratio of the pigment represented by the chemical formula (1) is 80% by mass or more and less than 100% by mass in the yellow coloring agent (A). Regarding.

The present invention also relates to the yellow colorant (A) containing at least one selected from the group consisting of a dye derivative having an acidic functional group and a resin type dispersant having an acidic functional group.

The present invention also relates to the yellow colorant (A), wherein the acidic functional group is at least one selected from the group consisting of a sulfo group, a carboxyl group and a phosphoric acid group.

The present invention also relates to a coloring composition comprising the yellow colorant (A), a binder resin, and a solvent.

The present invention also relates to the colored composition, which further comprises a red colorant.

The present invention also relates to the coloring composition, characterized by further comprising a polymerizable compound and/or a photopolymerization initiator.

The present invention also relates to a color filter formed from the coloring composition.

The present invention also relates to a sensor comprising the color filter.

Further, the present invention provides a yellow coloring agent having an average primary particle diameter of 100 nm or more and less than 300 nm containing a pigment represented by the following chemical formula (1) by solvent salt milling, and a yellow coloring agent having an average primary particle diameter of 30 nm or more and less than 100 nm. A method for producing a yellow coloring agent to obtain (A), characterized in that the yellow coloring agent (A) is boiled in distilled water and then filtered, and the resulting filtrate has a pH of 6.0 to 7.0. It relates to a method for producing a yellow colorant (A).

chemical formula (1)

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a yellow colorant that achieves both high tinting strength and high transmittance. Further, it is possible to provide a coloring composition having good stability when mixed with another coloring composition, and a color filter and sensor using the same.

Each constituent component of the present invention will be 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.).

<Yellow coloring agent (A)>
The yellow coloring agent (A) of the present invention is a yellow coloring agent (A) containing a pigment represented by the following chemical formula (1), and when the yellow coloring agent (A) is boiled in distilled water and filtered, The filtrate of is characterized by pH=6.0-7.0.

chemical formula (1)

The pH of the filtrate is evaluated and determined by the following method.
100 g of distilled water (purified water for batteries, manufactured by Mishima Shokusan Co., Ltd., pH=6.12) is added to 5 g of the colorant, and the mixture is boiled at 200° C. for 40 minutes. After boiling, add distilled water for the evaporated amount to make a total of 105 g. The resulting mixture of colorant and distilled water is filtered, and the pH of the filtrate is measured with a pH meter (D-51, manufactured by Horiba, Ltd.).

The yellow colorant (A) of the present invention can contain a pigment derivative and a resinous dispersant. The pH of the filtrate obtained when the colorant is boiled in distilled water and then filtered varies depending on the composition and blending amount of the pigment derivative and the resin-type dispersant used for the micronization. The decomposition of the pigment represented by the chemical formula (1) is suppressed by adjusting the composition and blending amount of the pigment derivative used for refining and the resin-type dispersant so that the pH is 6.0 to 7.0. , a yellow colorant (A) having a high tinting strength can be obtained.

(dye derivative)
A dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. Dye derivatives include, for example, compounds having acidic substituents such as sulfo, carboxy, or phosphate groups, and amine salts thereof, sulfonamide groups, or terminally basic substituents such as tertiary amino groups. compounds, and compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups.
Organic dyes include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, benzoiso Indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo and polyazo.

Specifically, diketopyrrolopyrrole-based dye derivatives, JP 2001-220520, WO2009/081930, WO2011/052617, WO2012/102399, JP 2017-156397, phthalocyanine Dye derivatives are disclosed in JP-A-2007-226161, WO2016/163351, JP-A-2017-165820, and Japanese Patent No. 5753266. Anthraquinone-based dye derivatives are disclosed in JP-A-63-264674 and JP-A-09. -272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325, quinacridone dye derivatives, JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383, dioxazine-based dye derivatives, JP-A-2011-162662, thiazineindigo-based dye derivatives, JP-A-2007-314785, triazine-based dye derivatives , JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681 , JP-A-2009-57478 for benzoisoindole-based dye derivatives, JP-A-2003-167112 for quinophthalone-based dye derivatives, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012 -226110, naphthol dye derivatives, JP 2012-208329, JP 2014-5439, azo dye derivatives, JP 2001-172520, JP 2012-172092, acidic Substituents, JP-A-2004-307854, basic substituents, JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404 The dye derivatives described are mentioned. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound. A compound having a substituent such as a neutral group is synonymous with a dye derivative.

These dye derivatives can be used singly or in combination of two or more.

By adding a pigment derivative to the pigment and performing pigmentation treatments such as acid pasting, acid slurry, dry milling, salt milling, and solvent salt milling, the pigment derivative is adsorbed on the surface of the pigment. In comparison, the primary particles of the pigment can be made finer.

The dye derivative can be used not only when the colorant is made finer, but also when the colored composition of the present invention, which will be described later, is produced.

When used for refining a yellow colorant containing a pigment represented by the chemical formula (1), the dye derivative can be added in an amount of 0 to 30 parts by mass with respect to 100 parts by mass of the pigment represented by the chemical formula (1). It is preferable to add 1 to 20 parts by mass, and more preferably 1 to 10 parts by mass.

As the dye derivative that may be contained in the yellow colorant (A) of the present invention, a dye derivative having an acidic functional group is preferable, and the acidic functional group is one or more of a sulfo group, a carboxyl group, and a phosphoric acid group. is more preferred. When adding a dye derivative having a basic functional group, it is preferable to add a resin-type dispersant having an acidic functional group, which will be described later.

(resin type dispersant)
The resin-type dispersant has a colorant-affinity site having a property of adsorbing to the added colorant and a site compatible with the colorant carrier, and adsorbs the added colorant to disperse to the colorant carrier. Anything can be used as long as it has a stabilizing function. Specifically, urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) 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 free carboxyl groups oil-based dispersants such as amides and their salts formed by the reaction with polyesters, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid Water-soluble resins such as copolymers, polyvinyl alcohol and polyvinylpyrrolidone, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide addition compounds, phosphate esters, etc. are used. It can be used alone or in combination of two or more.

Preferred examples of resin-type dispersants having an acidic functional group include resin-type dispersants having an aromatic carboxylic acid structure, which are disclosed in WO2008/007776, JP-A-2008-029901, JP-A-2009- 155406, JP-A-2010-185934, JP-A-2011-157416, JP-A-2009-251481, JP-A-2007-23195, JP-A-1996-143651, etc. Manufactured by known methods can do. A rosin-modified maleic acid resin is also a preferred example.

Examples of resin-type dispersants having basic functional groups include nitrogen atom-containing graft copolymers, and nitrogen dispersants having functional groups containing tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. in side chains. Examples include atom-containing acrylic block copolymers and urethane polymer dispersants.

Further, as disclosed in JP-A-2009-185277, a resin-type dispersant having an aromatic carboxyl group and a vinyl-based resin having a tertiary amino group (having the function of a resin-type dispersant) are combined. Combined use is also mentioned as an example.

The resin-type dispersant can be used not only when the colorant is made finer, but also when the colored composition of the present invention is produced.

When the resin-type dispersant is used for refining a yellow colorant containing a pigment represented by the chemical formula (1), it should be used in an amount of about 0 to 20% by mass with respect to the total amount of the pigment represented by the chemical formula (1). is preferred, and it is more preferred to use about 1 to 10% by mass.

The resin-type dispersant preferably has at least one functional group selected from the group consisting of a sulfo group, a carboxyl group, and a phosphoric acid group, and more preferably has an aromatic carboxylic acid structure as the carboxyl group.

(Other pigments)
The yellow colorant (A) of the present invention can contain other dyes within a range that does not impair the spectral properties of the compound represented by the chemical formula (1).

Other pigments may be contained in the yellow coloring agent (A), or may be added when preparing the coloring composition of the present invention.

The content ratio of the pigment represented by Chemical Formula (1) in the yellow colorant (A) of the present invention is preferably 80% by mass or more and less than 100% by mass.

<Method for producing yellow colorant (A)>
The yellow coloring agent (A) of the present invention has an average primary particle diameter of 30 nm or more by solvent-salt milling a yellow coloring agent having an average primary particle diameter of 100 nm or more and less than 300 nm containing a pigment represented by the chemical formula (1). Obtained as a yellow coloring agent (A) characterized in that the yellow coloring agent (A) is less than 100 nm and the filtrate obtained when the yellow coloring agent (A) is boiled in distilled water and filtered has a pH of 6.0 to 7.0. be able to.

Solvent salt milling is synonymous with salt milling treatment described later.

By refining a yellow coloring agent having a large average primary particle size of 100 nm or more and less than 300 nm by solvent salt milling, it can be made more uniform, and coloring power, transmittance, and dispersion stability can be improved in a well-balanced manner. can.

When the average primary particle size of the yellow colorant after being finely divided by solvent salt milling is 100 nm or more, the coloring power is high, but the transmittance is low. If the average primary particle size is less than 30 nm, the transmittance is improved, but the resistance is lowered. In addition, when the specific surface area of the coloring agent increases, the cohesive force increases, and the dispersibility and storage stability of the coloring composition deteriorate.

The average primary particle size was measured using a transmission electron microscope (TEM) H-7650 manufactured by Hitachi High-Technologies Co., Ltd. by directly measuring the size of the primary particles from an electron micrograph. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating a cube with the obtained particle size, and the volume average particle size was taken as the average primary particle size.

In order to obtain a suitable average primary particle size while suppressing decomposition of the pigment represented by the chemical formula (1), during solvent salt milling, the above-mentioned dye derivative having an acidic functional group and a resin type dispersion having an acidic functional group It is preferable to add at least one selected from the group consisting of agents.

As a yellow coloring agent containing a pigment represented by the chemical formula (1) having an average primary particle diameter of 100 nm or more and less than 300 nm, CINIC "Cinilex (R) Yellow SY3C
”, CINIC “Cinilex (R) Yellow SY3CN”, BASF “Paliotol (R) Yellow L2140HD”, BASF “Paliotol (R) Yellow K2142”, BASF “Paliotol (R) Yellow L2146HD”, etc. is mentioned.

<Coloring composition>
The coloring composition of the present invention is characterized by containing a yellow coloring agent (A), a binder resin, and a solvent. If necessary, the dye derivative, resin-type dispersant, and other dyes may be included. By subjecting these raw materials to dispersion treatment such as wet dispersion using two rolls, three rolls, or beads, for example, the dye derivative adsorbs to the surface of the pigment, and the surface of the pigment becomes polar, which promotes the adsorption of the resin-type dispersant. As a result, compatibility with pigments, dye derivatives, resin-type dispersants, solvents, and other additives is improved, and dispersion stability and viscosity stability over time of a colored composition are improved. Further, by improving the compatibility, the coating film has excellent temporal stability when the coloring composition is applied to a glass substrate or the like, and the waiting time from application of the coloring composition to exposure (PCD: Post Coating Delay) and exposure The stability and characteristic dependence of the pattern shape, etc., and the line width sensitivity stability with respect to the waiting time (PED: Post Exposure Delay) from the time to the heat treatment are improved. In addition, since the surface of the pigment is adsorbed and coated with the pigment derivative and the resin-type dispersant, it is possible to suppress the precipitation of crystals due to aggregation and sublimation of the pigment when the coating film is heated and baked. Further, variation in development time and development residue are suppressed.

(binder resin)
The binder resin is a resin having a transmittance of 80% or more in the entire wavelength range of 400-700 nm. In addition, the transmittance is preferably 95% or more. In terms of curing properties, binder resins include, for example, thermoplastic resins, thermosetting resins, active energy ray-curable resins, and the like. In addition, the active energy ray-curable resin may have an active energy ray-reactive functional group in a thermoplastic resin or a thermosetting resin. In terms of physical properties, binder resins include alkali-soluble resins and the like. Alkali solubility is for imparting development solubility in an alkali development step during production of a color filter, which will be described later, and an acidic group is required.

Binder resin can be used individually or in combination of 2 or more types.

Below, the binder resin that can be used in the coloring composition of the present invention will be described in detail.

[Thermoplastic resin]
Thermoplastic resins include, for example, acrylic resin, butyral resin, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd Resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.
Alkali-soluble thermoplastic resins include, for example, resins having acidic groups such as carboxyl groups and sulfone groups. Alkali-soluble thermoplastic resins include, for example, acrylic resins having acidic groups, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, and the like. Among these, an acrylic resin having an acidic group and a styrene/styrenesulfonic acid copolymer are preferred from the standpoint of improving developability, heat resistance and transparency.

[Active energy ray-curable alkali-soluble resin]
The active energy ray-curable alkali-soluble resin preferably has an ethylenically unsaturated double bond. Ethylenically unsaturated double bonds can be introduced, for example, by methods (i) and (ii) shown below. The resin is three-dimensionally crosslinked by the effect of the active energy ray, thereby increasing the crosslink density and improving chemical resistance.

[Method (i)]
Method (i) is, for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with another monomer, and adding an ethylenically unsaturated divalent A carboxyl group of unsaturated monobasic acid having a double bond is subjected to an addition reaction. Then, the produced hydroxyl group is reacted with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group.

Ethylenically unsaturated monomers having an epoxy group include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acid.

Unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl, alkoxyl, halogen, nitro, cyano substituted products of (meth)acrylic acid, etc. Carboxylic acid etc. are mentioned.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. In addition, if necessary, such as increasing the number of carboxyl groups, using a tricarboxylic anhydride such as trimellitic anhydride or using a tetracarboxylic dianhydride such as pyromellitic dianhydride, the remaining It is also possible to hydrolyze the anhydride group.

Other monomers include the following. 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, benzyl (meth)acrylate (meth)acrylates such as acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate;
Alternatively, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or (meth)acrylamide such as acryloylmorpholine Styrenes such as acrylamides styrene or 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 etc.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4- Phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimide Hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, N-substituted maleimides such as 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, phenyl ethoxylate Acrylates, ethylene oxide (EO)-modified (meth)acrylates of phenol, EO- or propylene oxide (PO)-modified (meth)acrylates of paracumylphenol, EO-modified (meth)acrylates of nonylphenol, PO-modified (meth)acrylates of nonylphenol, etc. are mentioned.

As a method similar to method (i), for example, an ethylenically unsaturated monomer having a carboxyl group and a part of the side chain carboxyl group of a copolymer obtained by copolymerizing another monomer 2) is a method of subjecting an ethylenically unsaturated monomer having an epoxy group to an addition reaction to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
Method (ii) is obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer, and adding an ethylenically unsaturated monomer having an isocyanate group to the side chain hydroxyl group of the copolymer. This is a method of reacting the isocyanate group of the monomer.

Ethylenically unsaturated monomers having a hydroxyl group are, for example, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, Hydroxyalkyl methacrylates such as glycerol mono(meth)acrylate or cyclohexanedimethanol mono(meth)acrylate can be mentioned. 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. 2-Hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred from the viewpoint of suppressing foreign matter on the coating film, and from the viewpoint of sensitivity, it is preferable to use one having 2 to 6 hydroxyl groups. is preferred, and glycerol mono(meth)acrylate is more preferred.

Ethylenically unsaturated monomers having an isocyanate group include, for example, 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate, and the like. be done.

Other monomers that can constitute the alkali-soluble resin include, in addition to the other ethylenically unsaturated monomers already described, N-substituted maleimides, alkyleneoxy group-containing monomers, and phosphate ester group-containing ethylenically unsaturated monomers. monomers, carboxyl group-containing ethylenically unsaturated monomers, and the like.
N-substituted maleimides include, for example, 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-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitro phenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine and the like. Examples of alkyleneoxy group-containing monomers include EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, and paracumylphenol. Examples include EO- or propylene oxide (PO)-modified (meth)acrylates, nonylphenol EO-modified (meth)acrylates, nonylphenol PO-modified (meth)acrylates, and the like.

As the carboxyl group-containing ethylenically unsaturated monomer, the monomers already described can be used.

The phosphate ester group-containing ethylenically unsaturated monomer is, for example, a compound obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphorylating agent such as phosphorus pentoxide or polyphosphoric acid. be.

[Alkali-soluble resin having no ethylenically unsaturated double bond]
The coloring composition herein can contain an alkali-soluble resin having no ethylenically unsaturated double bonds in order to adjust the degree of cure of the coating.

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 or more and 40,000 or less, preferably 3,000 or more and 30,000 or less, and 4,000, in order to impart alkali developing solubility. More than 20,000 or less is more preferable. Also, the value of Mw/Mn is preferably 10 or less. If the weight-average molecular weight (Mw) is less than 2,000, the adhesiveness to the substrate is lowered and the exposure pattern is less likely to remain. If it exceeds 40,000, the solubility in alkali development will be lowered, and a residue will be generated to deteriorate the linearity of the pattern.
The acid value of the alkali-soluble resin in the present invention is from 50 to 200 (KOHmg/g) in order to impart solubility in alkali development, preferably from 70 to 180, more preferably from 90 to 170. is. If the acid value is less than 50, the solubility in alkali development is lowered, and residues are generated, which deteriorates the linearity of the pattern. If it exceeds 200, the adhesion to the substrate will be lowered, and the exposure pattern will be difficult to remain.

Each raw material used for synthesizing the binder resin can be used alone or in combination of two or more.

[Thermosetting compound]
In the present invention, a thermosetting compound can be used in combination with the thermoplastic resin as the binder resin. When producing a color filter using the coloring composition of the present invention, by containing a thermosetting compound, it reacts during baking of the filter segment and increases the crosslink density of the coating film, so that the heat resistance of the filter segment is improved. Pigment agglomeration during baking of the filter segment is suppressed, and the effect of improving the contrast ratio can be obtained.

The thermosetting compound may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin.
Examples of thermosetting compounds include epoxy compounds, oxetane compounds, benzoguanamine compounds, melamine compounds, urea compounds, and phenolic compounds, but the present invention is not limited thereto. Epoxy compounds and oxetane compounds are preferably used in the coloring composition of the present invention.

The dye derivative used in preparing the colored composition is preferably added in an amount of 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and 3 to 10 parts by mass with respect to 100 parts by mass of the colorant. Adding is more preferable.

If a pigment derivative is not used when the yellow colored composition containing the pigment represented by Chemical Formula (1) is finely divided, it is preferable to add the pigment derivative when producing the colored composition.

The resin-type dispersant used in preparing the colored composition is preferably used in an amount of about 3 to 200% by mass with respect to the total amount of the coloring agent, and is preferably used in an amount of about 5 to 100% by mass from the viewpoint of film-forming properties. more preferred.

The content of the binder resin used in preparing the colored composition is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, with respect to 100 parts by mass of the coloring agent. When contained in an appropriate amount, a film can be easily formed, and good color characteristics can be easily obtained.

<Red colorant>
The colored composition of the present invention may further contain a red colorant. The red colorant is not particularly limited as long as it exhibits a red color, and may be a pigment or a dye.

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 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 JP-A-6368844, and the like. Among these, from the viewpoint of heat resistance, light resistance and transmittance of the filter segment, C.I. I. Pigment Red 48: 1, 122, 177, 224, 242, 254, 269, 272, 291, 295, 296, the pigment described in JP-A-2014-134712, the pigment described in Japanese Patent No. 6368844 Yes, more preferably C.I. I. Pigment Red 177, 254, 269, 272, 291, 295, 296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844.

Dyes include, for example, acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. In addition, dye derivatives and lake pigments obtained by converting dyes into lakes are also included.

<Other coloring agents>
The coloring composition of the present invention can contain other coloring agents as needed. Other colorants may be pigments or dyes, and may be used alone or in combination of two or more. Specific examples of organic pigments that can be used as other colorants are indicated by color index numbers, but are not limited to these.

(organic pigment)
Yellow pigments include, for example, 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, 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. Preferably C.I. I. Pigment Yellow 138, 150, 185, 231, 233, pigments described in JP-A-2012-226110.

As an orange pigment, C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73 and the like.

Examples of green pigments 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 pigments described in JP-A-2017-111398. Among these, from the viewpoint of transmittance, C.I. I. Pigment Green 36, 58, 59, 62, 63, a pigment described in JP-A-2017-111398.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, 81, etc. can. Among these, from the viewpoint of heat resistance, light resistance and transmittance of the filter segment, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6, more preferably C.I. I. Pigment Blue 15:6.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of heat resistance, light resistance and transmittance of the filter segment, C.I. I. Pigment Violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

Inorganic pigments include 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, and amber. , synthetic iron black, and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good applicability, sensitivity, developability, etc. while balancing chroma and lightness.

(Refinement of pigment)
When an organic pigment is used as a colorant, it is preferable to mix it with other raw materials after carrying out a refinement treatment. Examples of the method for the refinement treatment include wet grinding, dry grinding, dissolution precipitation, and the like. Among these, a salt milling treatment by a kneader method, which is one type of wet grinding, and the like are preferable.

The salt milling treatment is a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent, for example, a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. batch type or In this treatment, the mixture is mechanically kneaded while being heated using a continuous kneader, and then washed with water to remove the water-soluble inorganic salt and the water-soluble organic solvent. 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 water-soluble inorganic salts include sodium chloride, potassium chloride, sodium sulfate and the like. Among these, sodium chloride (table salt) is preferable from the point of price. The amount of the water-soluble inorganic salt to be used is preferably 50 to 2000 parts by mass, more preferably 300 to 1000 parts by mass, based on 100 parts by mass of the pigment, from the viewpoint of both processing efficiency and production efficiency.

The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt. A water-soluble organic solvent is a compound that dissolves (miscible in) water and does not substantially dissolve water-soluble inorganic salts. The water-soluble organic solvent is preferably a high boiling point solvent having a boiling point of 120° C. or higher because it is difficult to volatilize due to the temperature rise during salt milling. Water-soluble organic solvents include, 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, etc. mentioned. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.

A resin can be added as needed during the salt milling process. Resins include, for example, natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in water-soluble organic solvents.

(dye)
Dyes include, for example, acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. In addition, dye derivatives and lake pigments obtained by converting dyes into lakes are also included.

In addition, the dye is an acid dye having an acid group such as sulfonic acid or carboxylic acid, and in the case of a direct dye, an inorganic salt of an acid dye; an acid dye, a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or salt-forming compounds with primary amine compounds; and salt-forming compounds such as resin components having these amino groups and acid dyes. A salt-forming compound of an acid dye and a compound having an onium base is also preferable because of its excellent fastness. The compound having an onium base is preferably a resin having a cationic group in its side chain.

Examples of basic dyes include organic acids, perchloric acid, and salt-forming compounds with these metal salts. Among the salt-forming compounds, salt-forming compounds of basic dyes are preferable because they are excellent in various resistances and compatibility with pigments.

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.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine 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 dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and the like; Among these, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, Quinophthalone dyes, phthalocyanine dyes and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes and phthalocyanine dyes are more preferred. Specific structures of dyes are described in "Handbook of Dyes" (edited by Synthetic Organic Chemistry Society; Maruzen, 1970), "Color Index" (The Society of Dyers and Colorists), and "Dye Handbook" (edited by Okawara et al.; Kodansha, 1986). etc.

<Specific metal element>
The coloring composition of the present invention may contain small amounts of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) in addition to the constituent components of the pigment. Existence of a large amount of these specific metal elements may hinder storage stability, lower heat resistance, or lower sensitivity when prepared in the form of a photosensitive coloring composition described later.
In addition, a color filter prepared using a colored composition containing a large amount of such a specific metal element may generate foreign substances, and as a result, it is likely to cause a decrease in brightness. The total content of the specific metal elements contained in the coloring composition of the present invention is preferably 500 mass ppm or less.

The total amount of specific metal elements contained in the coloring composition of the present invention is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less. The lower limit of the total amount of the specific metal elements is not particularly limited, but is preferably 1 ppm by mass or more, more preferably 5 ppm by mass or more. If it is within the above range, it is possible to obtain a colored composition capable of suppressing costs, excellent in storage stability, and capable of forming a color filter with little generation of foreign matter and reduction in brightness.

The amount of each specific metal element contained in the coloring composition of the present invention is preferably 100 mass ppm or less, more preferably 50 mass ppm or less.

In addition, when metallic elements such as Ni, Zn, Cu, Al, Fe, and Co are included in a part of the pigment structure, these metallic elements that do not constitute a part of the pigment structure may be present. . Such metal elements should also be as small as possible, and can be removed in the same manner as the specific metal elements by the following method. Furthermore, it is preferable that the concentration of Mn, Cs, Ti, Co, Si, Pd, and the like mixed in with materials (for example, catalysts) used in the manufacturing process of various raw materials of the coloring composition is low.

Methods for removing pigments or metal elements mixed in from equipment during the manufacturing process include JP-A-2010-83997, JP-A-2018-36521, JP-A-7-198928, JP-A-8-333521, A method of washing with water as described in JP-A-2009-7432, etc., and a method of removing magnetic foreign matter using a magnet described in JP-A-2011-48736, etc., may be used singly or in combination.

The content of the specific metal element can be measured by inductively coupled plasma atomic emission spectrometry (ICP).

The coloring composition of the present invention can further contain a polymerizable compound and/or a photopolymerization initiator. Thereby, it can be used as a photosensitive coloring composition.

<Polymerizable compound>
The polymerizable compound contained in the coloring composition of the present invention includes monomers or oligomers that are cured by ultraviolet light, heat, or the like to form a transparent resin.

Polymerizable compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) Acrylates, 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, phenoxytetra Ethylene glycol (meth)acrylate, phenoxyhexaethyleneglycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, 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 Various acrylic and methacrylic esters such as melamine (meth)acrylate, epoxy (meth)acrylate, urethane acrylate, (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 and the like.

(Polymerizable compound having acid group)
The polymerizable compound can contain a photopolymerizable monomer having an acid group. Examples of acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups.

Photopolymerizable monomers having an acid group include, for example, polyhydric alcohols and (meth)acrylic acid esters of free hydroxyl group-containing poly(meth)acrylates and dicarboxylic acids; Examples thereof include esterified products with hydroxyalkyl (meth)acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. , malonic acid, succinic acid, glutaric acid, free carboxyl group-containing monoesters with dicarboxylic acids such as 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-hydroxy Monohydroxy monoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates, and the like can be mentioned.

(Polymerizable compound having urethane bond)
The polymerizable compound can contain a monomer having an ethylenically unsaturated bond and a urethane bond. The monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, or reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth)acrylate having a hydroxyl group. and polyfunctional urethane acrylates obtained by

(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, ) acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate , glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy(meth)acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

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

A polymerizable compound can be used individually or in combination of 2 or more types.

The blending amount of the polymerizable compound is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on 100% by mass of the non-volatile content of the coloring composition. Curability and developability are further improved when blended in an appropriate amount.

<Photoinitiator>
Photoinitiators include, 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 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, etc. Acetophenone compounds; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone , 4-benzoyl-4'-methyldiphenyl sulfide, or benzophenone compounds such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone , isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)- s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2 -piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(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 triazine compounds such as 2,4-trichloromethyl-(4′-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2- (O-benzoyloxime)], or oxime esters such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) Compounds; Phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. Among these, oxime ester compounds are preferred.

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

(Oxime ester compound)
In oxime ester-based compounds, the absorption of ultraviolet light causes cleavage of the NO bond of the oxime to produce iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the colorant concentration of the coloring composition is high, the ultraviolet transmittance of the coating film may be low and the degree of curing of the coating film may be low.

Oxime ester compounds are oximes described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. Ester-based photopolymerization initiators can be mentioned.

The content of the photopolymerization initiator is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass, with respect to 100 parts by mass of the colorant. When blended in an appropriate amount, the photocurability and developability are further improved.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine 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-acyloxyesters , acylphosphine oxide, methylphenylglyoxylate, 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 above sensitizers, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives can be mentioned as sensitizers capable of particularly suitable sensitization. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

More specifically, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al. Special Functional Materials" (CMC, 1986), but not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be included.

A sensitizer can be used alone or in combination of two or more.

The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator. When contained in an appropriate amount, curability and developability are further improved.

<Thiol chain transfer agent>
The coloring composition of the present invention preferably contains a thiol chain transfer agent as a chain transfer agent. By using a thiol together with a photopolymerization initiator, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen, so the resulting colored composition has high sensitivity. .

Moreover, polyfunctional aliphatic thiols bonded to aliphatic groups such as methylene and ethylene groups having two or more thiol groups are preferred. More preferred are polyfunctional aliphatic thiols having 4 or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and it is possible to cure from the surface of the pattern to the vicinity of the substrate.

Polyfunctional thiols include, for example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropio trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s- Examples include triazines, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

A thiol-based chain transfer agent can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 0.1 to 10% by mass, more preferably 0.1 to 3% by mass, based on 100% by mass of the nonvolatile matter of the coloring composition. When contained in an appropriate amount, the photosensitivity and tapered shape are improved, and wrinkles are less likely to occur on the coating surface.

<Polymerization inhibitor>
The coloring composition can contain a polymerization inhibitor. This makes it possible to suppress exposure due to diffracted light from the mask during photolithographic exposure, making it easier to obtain a pattern of a desired shape.

Examples of polymerization inhibitors include 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-tert-butylcatechol, 3-tert-butylcatechol, 4- Alkylcatechol compounds such as tert-butylcatechol and 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propyl Alkylresorcinol compounds such as resorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, Alkylhydroquinone compounds such as 2,5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine and tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide, etc. phosphine oxide compounds, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, phloroglucine and the like.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass based on 100% by mass of the non-volatile content of the coloring composition. Within this range, the effect of the polymerization inhibitor is increased, and the straightness of the taper, the wrinkles of the coating film, the pattern resolution, etc. are improved.

<Ultraviolet absorber>
The coloring composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorption function, and includes benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds. .

The content of the ultraviolet absorber is preferably 5 to 70% by weight based on the total 100% by weight of the photopolymerization initiator and the ultraviolet absorber. When contained in an appropriate amount, the resolution after development is further improved.

Further, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the non-volatile content of the coloring composition. When contained in an appropriate amount, the adhesion between the substrate and the film is further improved, and good resolution can be obtained.

Benzotriazole compounds include 2-(5-methyl-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-dimethyl ethyl)-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. In addition, oligomer type and polymer type compounds having a benzotriazole structure can also be used.

Triazine compounds include 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-dihydroxyphenyl )-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidate ester reaction product, 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-(hexyl oxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine and the like. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.

Benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2 , 2′,4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

Salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tertbutylphenyl salicylate. In addition, oligomer type and polymer type compounds having a salicylic acid ester structure can also be used.

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the coloring composition from oxidizing and yellowing due to the thermal process during thermal curing and ITO annealing, so that the transmittance of the coating film can be improved. . In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film cross-linking component is reduced, so measures such as using a highly sensitive cross-linking component and increasing the amount of the photopolymerization initiator cause yellowing during the heat process. can be seen. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and to obtain a high transmittance of the coating film.

Antioxidants include, for example, hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In this specification, the antioxidant is preferably a compound containing no halogen atom.

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

An antioxidant can be used individually or in combination of 2 or more types.

Further, the content of the antioxidant is more preferably 0.5 to 5.0% by mass based on 100% by mass of the solid content of the coloring composition, because the transmittance, spectral characteristics, and sensitivity are good.

<Leveling agent>
A leveling agent is preferably added to the colored composition of the present invention for the purpose of improving the coating properties of the composition on a transparent substrate and the drying properties of the colored film. Various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants and anionic surfactants can be used as the leveling agent.

When the coloring composition of the present invention contains a surfactant, the amount of surfactant added is preferably 0.001 to 2.0% by mass, more preferably, based on the total solid content of the composition of the present invention. is 0.005 to 1.0% by mass. Within this range, the coating properties of the coloring composition, the pattern adhesion, and the transmittance are well balanced.
The coloring composition of the present invention may contain only one type of surfactant, or may contain two or more types of surfactants. When two or more types are included, the total amount is preferably within the above range.

<Storage stabilizer>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Storage stabilizers 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, tetraphenylphosphine and the like. organic phosphines, phosphites, and the like. The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the coloring agent (100% by mass).

<Adhesion improver>
The coloring composition of the present invention may contain an adhesion improver such as a silane coupling agent in order to improve adhesion to the substrate. By improving the adhesion with the adhesion improving agent, the reproducibility of fine lines is improved and the resolution is improved.

Examples of adhesion improvers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- (Meth)acrylsilanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane Silane, 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-mercaptopropylmethyldimethoxy mercaptos such as silane, 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureides such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide and silane coupling agents such as isocyanates such as , 3-isocyanatopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the colorant in the coloring composition. Within this range, the effect is enhanced and the balance between adhesion, resolution, and sensitivity is good, which is more preferable.

<Solvent>
The coloring composition of the present invention contains a solvent in order to facilitate the formation of a colored film by coating it on a substrate such as glass to a dry film thickness of 0.2 to 5 μm. The solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

As the solvent, a solvent commonly used in the field can be used. Considering the performance such as boiling point, SP value, evaporation rate, viscosity, etc., it can be used alone or as appropriate according to the coating conditions (speed, drying conditions, etc.). used in combination.

Solvents used include, for example, ester solvents (solvents containing -COO- in the molecule but not containing -O-), ether solvents (solvents containing -O- in the molecule but not containing -COO-) , ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule but not containing -COO-), alcohol solvents (solvents containing OH in the molecule solvents that do not contain -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

Among the above solvents, it is preferable to include an organic solvent having a boiling point of 120° C. or higher and 180° C. or lower at 1 atm from the viewpoint of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2- Pentanone, N,N-dimethylformamide, N-methylpyrrolidone and the like are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are more preferred.

<Method for producing a photosensitive coloring composition>
The coloring composition of the present invention contains a coloring agent, a dispersing agent, a coloring agent carrier such as a binder resin, and/or a solvent, preferably together with a dispersing aid (pigment derivative or surfactant), kneader, two kneaders. It can be produced by finely dispersing using various dispersing means such as a roll mill, three-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or attritor (colorant dispersion). At this time, two or more kinds of coloring agents and the like may be dispersed in the coloring agent carrier at the same time, or may be mixed separately dispersed in the coloring agent carrier. If the colorant such as dye has high solubility, specifically, if it has high solubility in the solvent to be used, and if it is dissolved by stirring and no foreign matter is confirmed, it is manufactured by finely dispersing as described above. No need.

When used as a photosensitive colored composition (resist material), it can be prepared as a solvent-developable or alkali-developable colored composition. The solvent-developable or alkali-developable colored composition comprises the above-mentioned colorant dispersion, a photopolymerizable monomer and/or a photopolymerization initiator, and optionally a solvent, other dispersing aids, and additives. etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Removal of coarse particles>
The coloring composition of the present invention is separated from coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.1 μm or more, by means of centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or a membrane filter, or the like. It is preferable to remove coarse particles of 5 μm or more and mixed dust. Thus, the coloring composition preferably does not substantially contain particles of 0.5 μm or larger. More preferably, it is 0.3 μm or less.

<Water content in the coloring composition>
The coloring composition of the present invention preferably has a water content of 2% by mass or less with respect to the total amount of the coloring composition.

When the water content is within the above range, the coloring composition is excellent in dispersion stability and sensitivity even after being stored for a long time.

The content of water is preferably 1.8% by mass or less, more preferably 1.6% by mass or less, relative to the total amount of the coloring composition. If the water content is sufficiently small within this range, problems with the dispersion stability and sensitivity of the coloring composition are less likely to occur even after long-term storage.

A method for controlling the water content is not particularly limited, and a known method can be used. Examples thereof include a method of producing a colored composition while blowing in a dry inert gas, and a method of adding molecular sieves and dehydrating after production. Among them, the method of manufacturing while blowing dry inert gas is preferable.

The water content can be measured by a known method such as the Karl Fischer method.

<Color filter>
Next, the color filter of the present invention will be explained.
The color filter of the present invention comprises a red filter segment, a green filter segment and a blue filter segment. Also, the color filter may further comprise a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment.

(Manufacturing method of color filter)
A color filter can be manufactured by a printing method or a photolithographic method.
Formation of filter segments by a printing method can be patterned simply by repeating printing and drying of a coloring composition prepared as a printing ink, and therefore, as a method for producing color filters, it is low cost and excellent in mass productivity. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to have a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, it is also important to control the fluidity of the ink on the printing press, and it is also possible to adjust the viscosity of the ink using a dispersant or an extender.

When the filter segment is formed by photolithography, the colored composition prepared as the solvent-developable or alkali-developable colored resist material is applied onto the transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. Depending on the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed (irradiated with radiation) through a mask having a predetermined pattern provided in contact or non-contact with the film. After that, the film is immersed in a solvent or alkaline developer or sprayed with a developer to remove the uncured portion to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to promote polymerization of the colored resist material, heating may be applied as necessary. According to the photolithography method, it is possible to manufacture a color filter with higher precision than the printing method.

At the time of development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoaming agent or a surfactant can be added to the developer.
In order to increase the exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is coated and dried to form a film that prevents polymerization inhibition by oxygen. , exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method, etc. in addition to the above methods, and the colored composition of the present invention can be used in any of these methods. The electrodeposition method is a method of manufacturing a color filter by using a transparent conductive film formed on a substrate to electrodeposit each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which filter segments are formed in advance on the surface of a removable transfer base sheet, and the filter segments are transferred to a desired substrate.

A black matrix can be formed in advance before forming each color filter segment on the transparent substrate or the reflective substrate. As the black matrix, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed can be used, but is not limited to these. Alternatively, thin film transistors (TFTs) may be formed in advance on the transparent substrate or reflective substrate, and then each color filter segment may be formed. An overcoat film, a transparent conductive film, and the like are formed on the color filter of the present invention, if necessary.

The color filter of the present invention can also be used for manufacturing color liquid crystal display devices, color solid-state imaging devices, organic EL display devices, quantum dot display devices, electronic paper, and the like.

<Sensor>
The sensor of the invention comprises the color filter segment of the invention. The configuration of the sensor of the present invention is a configuration provided with the color filter segment of the present invention, and is not particularly limited as long as it functions as a sensor. Examples of the configuration include the following.
A plurality of photodiodes constituting a light receiving area of a solid-state imaging device (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) and transfer electrodes made of polysilicon or the like are provided on a substrate, and on the photodiodes and the transfer electrodes, A light shielding film made of tungsten or the like with an opening only in the light receiving portion of the photodiode, and a device protective film 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 is a configuration having the color filter of the present invention on the device protective film.
Furthermore, a configuration having a condensing means (for example, a microlens or the like; the same shall apply hereinafter) above the device protective layer and below the color filter (on the side close to the substrate), or a configuration having a condensing means above the color filter, etc. may be
The organic CMOS sensor includes a thin panchromatic photosensitive organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate. It is a two-layered hybrid structure in which inorganic materials play the role of extracting signals to the outside, and in principle, it is possible to achieve an aperture ratio of 100% for incident light. Since the organic photoelectric conversion film is a structure-free continuous film and can be laid on a CMOS signal readout substrate, it does not require an expensive microfabrication process and is suitable for miniaturization of filter segments.
Arrangement of the color filters is not particularly limited, and a known method can be used.

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited by these. In the examples, "parts" and "%" represent "parts by weight" and "% by weight", respectively.

In addition, the polymerization average molecular weight (Mw) of the resin-type dispersant having an acidic functional group is determined by GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation). is a polystyrene equivalent weight average molecular weight (Mw) measured using THF. The solid content is a solid content measurement value obtained from the weight loss on drying when 0.5 g of a solution of a resin-type dispersant is accurately weighed and placed in a dryer at 180° C. for 20 minutes.

The acid value of the resin-type dispersant having an acidic functional group was determined by potentiometric titration using a 0.1N potassium hydroxide/ethanol solution. The acid value of resin indicates the acid value of non-volatile matter.

The weight-average molecular weight (Mw) of the resin-type dispersant having a basic functional group was measured by GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation). It is a polystyrene-equivalent weight average molecular weight (Mw) measured using an N,N-dimethylformamide solution of 3 mM triethylamine and 10 mM LiBr.

The amine value of the resin-type dispersant having a basic functional group was obtained by potentiometric titration using 0.1N hydrochloric acid aqueous solution, and then converted to the equivalent of potassium hydroxide. The amine value of the resin indicates the amine value of the non-volatile matter.

The quaternary ammonium salt value of the resin-type dispersant having a basic functional group was determined by titration with a 0.1 N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted to the equivalent of potassium hydroxide. . The quaternary ammonium salt value of the resin indicates the quaternary ammonium salt value of the non-volatile matter.

First, the dye derivatives used in Examples and Comparative Examples have the following structures.

(Dye derivative (C1))

(Dye derivative (C2))

(Dye derivative (C3))

(Dye derivative (C4))

(Dye derivative (C5))

(Dye derivative (C6))

(Dye derivative (C7))

Next, methods for producing the resin type dispersant, the binder resin, the red coloring agent and the red coloring composition used in Examples and Comparative Examples will be described.

<Method for producing binder resin or resin-type dispersant>
(Preparation of binder resin (B1))
A separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and after replacing the inside of the flask with nitrogen, the distillate was added from the dropping tube. A mixture of 18 parts of cyclopentanyl methacrylate, 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. . After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, then a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container was changed to air exchange, and 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of the glycidyl groups), and the mixture was heated at 120°C. The reaction was continued for 6 hours, and when the solid content acid value reached 0.5, the reaction was terminated to obtain a solution of an acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. A binder resin (B1) was prepared by adding acetate. The weight average molecular weight (Mw) was 19,000.

(Preparation of resin type dispersant (B2) having acidic functional group)
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 propylene glycol monomethyl ether acetate are charged into a reaction vessel equipped with a gas inlet tube, temperature, condenser, and stirrer, and nitrogen gas is introduced. replaced with
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 obtained by adding 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate. Solid content measurement confirmed that 95% had reacted.
19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and heated at 100°C. The reaction was allowed to proceed for 7 hours. After confirming that 98% or more of the acid anhydride is half-esterified by measuring the acid value, the reaction is terminated. A resin-type dispersant (B2) having an acidic functional group with a molecular weight of 70 mgKOH/g and a weight average molecular weight of 8,500 was obtained.

(Preparation of resin type dispersant (B3) having basic functional group)
40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, and the mixture was heated at 50°C while flowing nitrogen. After stirring for 1 hour, the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 133 parts of methoxypropyl acetate are charged, and the temperature is raised to 110° C. under a nitrogen stream to give the first block (B block) was initiated. After polymerization for 4 hours, the polymerization solution was sampled and solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile matter. Next, 61 parts of methoxypropyl acetate, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were added to this reactor, and the reaction was carried out at 110°C under a nitrogen atmosphere. Stirring was maintained and the reaction was continued. Two hours after the addition, the polymerization solution was sampled and the solid content was measured to confirm that the polymerization conversion rate of the second block (A block) was 98% or more in terms of the non-volatile matter. Polymerization was stopped by cooling. As a result of GPC measurement, the polymer had a mass average molecular weight of 20,000, a molecular weight distribution Mw/Mn of 1.4, and a reaction conversion rate of 98.5%. Thus, a resin solution having an amine value per solid content of 169.8 mgKOH/g was obtained. After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether acetate is added so that the nonvolatile content becomes 40% by mass. A resin-type dispersant (B3) with functional groups was prepared.

[Production Example 1-1]
<Production of red colorant>
95 parts of diketopyrrolopyrrole red pigment PR254 ("Irgaphor Red S 3610 CF" manufactured by BASF), 5 parts of pigment derivative (C5), 1000 parts of crushed salt, and 180 parts of diethylene glycol were added to a stainless steel 1 gallon kneader (Inoue Seisakusho ) and kneaded at 60°C for 8 hours. This mixture is poured into 2000 parts of warm water, heated to about 60° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent, and then heated at 80° C. for 24 hours. Dried to obtain 100 parts of red colorant (PR-1).

[Production Example 2-1]
<Method for producing red colored composition>
After uniformly stirring and mixing a mixture of 91 parts of a red colorant (PR-1), 9 parts of a pigment derivative (C5), 60 parts of a resin type dispersant (B2) having an acidic functional group, and 460 parts of propylene glycol monomethyl ether acetate. , zirconia beads having a diameter of 0.5 mm were dispersed in an Eiger mill for 2 hours, and then filtered through a 5 μm filter to prepare a red colored composition (DR-1).

[Example 1-1]
<Production of yellow colorant>
100 parts of isoindoline-based yellow pigment PY139 ("Cinilex (R) Yellow SY3C" manufactured by CINIC), 1000 parts of crushed salt, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60°C for 8 hours. Time kneaded. This mixture is poured into 2000 parts of warm water, heated to about 60° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent, and then heated at 80° C. for 24 hours. Dried to obtain 100 parts of a yellow colorant (PY-1).

[Example 1-2] to [Example 1-63], [Comparative Example 1-1] to [Comparative Example 1-9]
Kneading, purification, and drying were performed under the same conditions as in Example 1-1 except that the pigment, dye derivative C, binder resin B, or resin type dispersant B was added at the ratio shown in Table 1, and a yellow coloring agent ( PY-2) to (PY-72) were obtained. The parts by weight of the binder resin B or the resin-type dispersant B in Table 1 indicate the parts by weight of the solid content.

Marquid 32 in Table 1 is a rosin-modified maleic acid resin (Marquid No. 32, acid value 130, weight average molecular weight 1000, manufactured by Arakawa Chemical Co.), which is a resin-type dispersant having an acidic functional group, and D1155 is BASF. manufactured by Paliotol® Yellow D1155.

Further, the pigments represented by the chemical formula (1) in Table 1 are as follows.
SY3CN: “Cinilex (R) Yellow SY3CN” manufactured by CINIC, average primary particle size 150 to 200 nm
L2140HD: BASF "Paliotol (R) Yellow L2140HD", average primary particle size 150 to 200 nm
K2142: "Paliotol (R) Yellow K2142" manufactured by BASF, average primary particle size 150 to 200 nm
L2146HD: BASF "Paliotol (R) Yellow L2146HD", average primary particle size 200 to 250 nm
D1819: BASF "Paliotol (R) Yellow D1819", average primary particle size 50 to 80 nm
K1841: "Paliotol (R) Yellow K1841" manufactured by BASF, average primary particle size 50 to 80 nm
H2R: “Graphtol (R) Yellow H2R” manufactured by CLARIANT, average primary particle size 50 to 80 nm

[pH measurement of yellow colorant]
After boiling the yellow colorants (PY-1) to (PY-72) with distilled water, the pH of the filtered filtrate was measured under the following condition (X).

Condition (X)
100 g of distilled water is added to 5 g of coloring agent, and the mixture is boiled at 200° C. for 40 minutes. After boiling, add distilled water for the evaporated amount to make a total of 105 g. The resulting mixture of colorant and distilled water was filtered using No. 5C filter paper (manufactured by Toyo Roshi Kaisha, Ltd.), and the pH of the filtrate was measured using a pH meter (D-51, manufactured by Horiba Ltd.). Measured at

[Example 2-1] to [Example 2-66], [Comparative Example 2-1] to [Comparative Example 2-9]
<Method for producing yellow colored composition>
After uniformly stirring and mixing the mixture of the composition (parts by weight) shown in Table 2, using zirconia beads with a diameter of 0.5 mm, after dispersing with an Eiger mill for 2 hours, it was filtered through a 5 μm filter to give a yellow colored composition (DY -1) to (DY-66) and (DY-67) to (DY-75) were produced. In Table 2, the parts by weight of the resin type dispersant B are the parts by weight of the solid content, and the parts by weight of PGMAc are the parts by weight including the PGMAc contained in the resin type dispersant B.

PGMAc in Table 2 represents propylene glycol monomethyl ether acetate.

[Example 2-67] to [Example 2-69]
<Method for producing red colored composition>
After uniformly stirring and mixing the mixture of the composition (parts by weight) shown in Table 2, using zirconia beads with a diameter of 0.5 mm, after dispersing with an Eiger mill for 2 hours, it was filtered through a 5 μm filter to give a red colored composition (DYR -1) to (DYR-3) were produced.

[Example 3-1] to [Example 3-69], [Comparative Example 3-1] to [Comparative Example 3-9]
<Method for producing a photosensitive coloring composition>
A mixture having the composition (parts by weight) shown in Table 3 was uniformly stirred and mixed, and then filtered through a 1 μm filter to prepare photosensitive coloring compositions (RR-1) to (RR-78). The parts by weight other than PGMAc in Table 3 represent the parts by weight of the solid content excluding PGMAc. Further, the coloring compositions 1 and 2 were mixed at a total of 14.88 parts by mass by changing the mixing ratio so that the transmittance at 530 nm was 5% when the transmittance at 400 nm was 5%. .

PGMAc in Table 3 represents propylene glycol monomethyl ether acetate. Further, the photopolymerizable monomer M-402 is dipentaerythritol hexaacrylate ("Aronix M-402" manufactured by Toagosei Co., Ltd.), and the photopolymerization initiator OXE-01 is 1,2-octanedione, 1- represents [4-(phenylthio)phenyl-,2-(O-benzoyloxime)] (IRGACURE OXE-01 manufactured by BASF Japan).

<Evaluation>
[Mixing stability]
The mixing stability of the resulting photosensitive coloring composition was evaluated in three grades according to the following criteria.
○: Viscosity increase rate when stored at 40 ° C. for 1 week is less than 103% △: Viscosity increase rate when stored at 40 ° C. for 1 week is 103% or more and less than 105% ×: When stored at 40 ° C. for 1 week The viscosity increase rate of 105% or more

[Color strength evaluation]
The obtained photosensitive coloring composition was coated on a 6-inch silicon wafer with a flattening film resist solution (HL-18s: manufactured by Nippon Steel Chemical Co., Ltd.) by spin coating, and pre-baked at 100 ° C. hot. The plate was heat treated for 6 minutes. Further, the coated film was cured in an oven at 230° C. for 1 hour to form a 1.0 μm flattening film to obtain a wafer with a flattening film. Next, the resulting resist material was applied onto a silicon wafer with a flattening film by a spin coater, and as a pre-bake, heat treatment was performed on a hot plate at 100° C. for 1 minute. Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), pattern exposure was performed at a wavelength of 365 nm at an exposure amount of 150 mJ/cm through a photomask for forming 1.0 μm square pixels. gone. The exposed coating film was puddle-developed with an organic alkaline developer for 1 minute. After the puddle development, it was rinsed with pure water for 20 seconds using a spin shower, and then washed with pure water for 20 seconds. After that, water droplets remaining on the wafer were blown off with high-pressure air, and the substrate was naturally dried to form a square pixel pattern. Then, it was heated and dried at 230° C. for 60 minutes to prepare an evaluation substrate. At the time of preparation, adjustment was made by changing the rotation speed of spin coating so that the transmittance at 530 nm was 5%.
The coloring strength of this coating film was evaluated in three grades according to the following criteria.
○: film thickness is less than 0.55 μm
Δ: film thickness is 0.55 μm or more and less than 0.60 μm ×: film thickness is 0.60 μm or more

[Transmittance evaluation]
The transmittance of the previous coating film was evaluated in three grades according to the following criteria.
○: Transmittance at 600 nm is 90% or more △: Transmittance at 600 nm is 85% or more and less than 90% ×: Transmittance at 600 nm is less than 85%

As described above, the yellow coloring composition containing the pigment represented by the chemical formula (1), the filtrate obtained by boiling after boiling with distilled water and filtering the yellow coloring agent has a pH of 6.0 to 7.0. By using the product, it is possible to obtain a photosensitive coloring composition that has good mixing stability with a red coloring composition and also has good coloring power and transmittance.

Furthermore, by using these photosensitive coloring compositions, it is possible to provide a color filter for an image sensor with improved film thickness, improved color separation, and improved color reproducibility, and a sensor.

Claims (10)

A yellow coloring agent (A) containing a pigment represented by the following chemical formula (1), wherein the yellow coloring agent (A) is boiled in distilled water and filtered, and the filtrate has a pH of 6.0 to 7. A yellow colorant (A) characterized by .0.

chemical formula (1)

2. The yellow coloring agent (A) according to claim 1, wherein the content of the pigment represented by the chemical formula (1) is 80% by mass or more and less than 100% by mass in the yellow coloring agent (A). 3. The yellow colorant (A) according to claim 1 or 2, comprising at least one selected from the group consisting of a dye derivative having an acidic functional group and a resin type dispersant having an acidic functional group. 4. The yellow coloring agent (A) according to claim 3, wherein the acidic functional group is at least one selected from the group consisting of a sulfo group, a carboxyl group and a phosphate group. A coloring composition comprising the yellow colorant (A) according to any one of claims 1 to 4, a binder resin, and a solvent. 6. The colored composition of claim 5, further comprising a red colorant. 7. The colored composition according to claim 5, further comprising a polymerizable compound and/or a photopolymerization initiator. A color filter characterized by being formed from the colored composition according to any one of claims 5 to 7. A sensor comprising a color filter according to claim 8 . Solvent salt milling a yellow coloring agent having an average primary particle diameter of 100 nm or more and less than 300 nm containing a pigment represented by the following chemical formula (1) to obtain a yellow coloring agent (A) having an average primary particle diameter of 30 nm or more and less than 100 nm Yellow A method for producing a coloring agent, wherein the yellow coloring agent (A) is boiled in distilled water and then filtered, and the resulting filtrate has a pH of 6.0 to 7.0. Production method.

chemical formula (1)