TW202235456A - Colored resin composition, colored film, and decorative substrate - Google Patents

Abstract

Provided is a colored resin composition comprising (A) a resin containing a hydroxyl group or an acid group, (B) a colorant, (C) a dispersant, and (D) a blocked isocyanate, wherein the dispersant (C) is an acrylic dispersant having a basic group. The colored resin composition can cure at low temperatures and has excellent viscosity stability at ordinary temperature. The colored resin composition, even after a light-resistance test or a high-temperature high-humidity test, retains high adhesiveness.

Description

Colored resin composition, colored film, decorative substrate

The invention relates to a colored resin composition, a colored film and a decorative substrate.

Regarding touch panels in various information terminals such as smartphones and car displays, a light-shielding film is formed on the non-display area of the cover lens located on the outermost layer when viewed from the user side, and the light-shielding film is responsible for shielding the touch sensor. The role of electrodes such as traction wiring.

In car monitors and smart watches, it is required that the reliability of operation or design will not change even under the ultraviolet radiation of sunlight or high temperature and high humidity environment, and it is required to be used in such an environment even in the light shielding film covering the lens The lower adhesion does not decrease, etc.

In addition, especially in in-vehicle displays, resins such as polycarbonate may be used as the material of the cover lens. As a method of forming a light-shielding film on a resin, there is a method of directly printing ink on the resin by screen printing, inkjet printing, gravure printing, or a method of manufacturing a cover lens by in-mold molding of a decorative film. Either way, since the heat resistance of the base material is lower than that of glass, an ink that can be cured under low-temperature sintering at 80°C to 120°C is required. In addition, in these printing methods, from the viewpoint of continuous printability and film thickness reproducibility, it is required that the viscosity does not change at normal temperature.

Therefore, for example, in Patent Document 1, an ink for inkjet printing is studied. The ink for inkjet printing contains: a carboxyl group-containing binder polymer with a weight average molecular weight of 20,000 to 300,000, and a blocked isocyanate and epoxy resin. Hardener for resins. In addition, in Patent Document 2, as an ink that can be printed on a non-heat-resistant non-absorbing medium and can be cured at low temperature, an acrylic resin containing a glycol ether-based solvent and an acetate-based solvent and containing a hydroxyl group and a low-temperature curing ink have been studied. Ink for inkjet printing that dissociates blocked isocyanate. [Prior art literature] [Patent Document]

Patent Document 1: International Publication No. 2018/155500 Patent Document 2: Japanese Patent Laid-Open No. 2016-138229

[Problem to be Solved by the Invention]

However, the ink described in Patent Document 1 can maintain high adhesion after various reliability tests by using both blocked isocyanate and epoxy resin, but since the epoxy resin reacts with the carboxyl group of the polymer, etc., Since the film thickness and printing accuracy change when used for long-term printing, the viscosity stability is insufficient. In addition, the ink described in Patent Document 2 can be cured at low temperature and has excellent viscosity stability, but its adhesiveness deteriorates after rigorous reliability tests of automotive standards, and its characteristics are insufficient in terms of light resistance and high-temperature and high-humidity resistance.

Therefore, the object of the present invention is to provide a colored resin composition that can be cured at low temperature, has excellent viscosity stability at room temperature, and maintains high adhesion even after a light resistance test and a high temperature and high humidity test. [Means to solve the problem]

The inventors of the present invention have conducted diligent research and found that by making the colored resin composition contain a resin containing hydroxyl or acid groups, a coloring material, a dispersant, and a blocked isocyanate, and using an acrylic dispersion having a basic group, As a dispersant, the above problems can be solved, and the present invention has been completed.

That is, the object of the present invention is mainly achieved by the following structures. A colored resin composition, containing (A) resin containing hydroxyl or acid groups, (B) coloring material, (C) dispersant and (D) blocked isocyanate, the (C) dispersant is Acrylic dispersant. [Effect of the invention]

The colored resin composition of the present invention can be cured at low temperature, has excellent viscosity stability at room temperature, and can maintain high adhesion after a light resistance test and a high temperature and high humidity test.

Hereinafter, the present invention will be described in more detail.

The colored resin composition of the present invention contains (A) hydroxyl or acid group-containing resin, (B) coloring material, (C) dispersant, and (D) blocked isocyanate. (A) The resin containing a hydroxyl group or an acid group functions as a binder in the composition. (B) The coloring material has the effect of shielding visible light. (C) The dispersant has the function of uniformly dispersing the coloring material and preventing re-agglomeration. (D) The blocked isocyanate has an effect of reacting only with hydroxyl groups or acid groups contained in the resin when heated and kneaded.

The present invention is characterized in that the (C) dispersant is an acrylic dispersant having a basic group. The acrylic dispersant is excellent in reliability such as light resistance and high temperature and high humidity resistance. Furthermore, since the dispersant has a basic group, the dispersant is adsorbed on the surface of the coloring material, and when the coloring material is dispersed, the coloring material is finely dispersed, and the dispersion state is stabilized by the steric barrier between the dispersing agents, thereby having the effect of inhibiting the process. Viscosity or re-agglomeration. In addition, (D) blocked isocyanate is non-reactive at room temperature due to the function of the blocking agent, and is only reactive when heated, so it can maintain the viscosity stability of the colored resin composition well. By properly selecting End-capping agent, the end-capping agent dissociates at low temperature and can react with hydroxyl or acid groups.

(A) The resin containing a hydroxyl group or an acid group is a resin having a hydroxyl group or an acid group. (A) Resins containing hydroxyl groups or acid groups include, for example, acrylic resins, cardo resins, silicone resins, polyimide resins, polyimide precursors, polyurethane resins, polyester resins, Ester resin, vinyl chloride resin, etc. Two or more of these may be contained. Among these, from the viewpoint of the storage stability of the colored resin composition or the adhesiveness and reliability of the colored film, an acrylic resin, a polyurethane resin, or a polyester resin is preferable, and an acrylic resin is particularly preferable. .

From the viewpoint of the viscosity stability, curing speed, adhesion of the colored film, and the reliability of the colored film of the colored resin composition, (A) the resin containing a hydroxyl group or an acid group preferably has a hydroxyl value or an acid value of 10 mgKOH /g or more. The hydroxyl value is preferably from 20 mgKOH/g to 300 mgKOH/g, more preferably from 90 mgKOH/g to 250 mgKOH/g. The acid value is preferably 20 mgKOH/g-300 mgKOH/g, more preferably 60 mgKOH/g-150 mgKOH/g. The total of the acid value and the hydroxyl value is preferably from 80 mgKOH/g to 300 mgKOH/g, more preferably from 100 mgKOH/g to 300 mgKOH/g. When the total of acid value and hydroxyl value is less than 80 mgKOH/g, the number of functional groups reacting with (D) blocked isocyanate decreases, so there is a decrease in the curing speed, or the adhesion of the colored film and various reliability tests. Risk of poor adhesion. Moreover, when the sum total of an acid value and a hydroxyl value is less than 80 mgKOH/g, the fall of viscosity stability and the raise of the diffuse reflectance of the coloring film obtained were confirmed. It is believed that the decrease in the viscosity stability and the increase in the diffuse reflectance of the colored film are caused by the fact that (A) the compatibility of the hydroxyl or acid group-containing resin with (D) the blocked isocyanate is deteriorated, (D) The blocked isocyanate inhibits the dispersion of the coloring material. When the colored film is formed in the non-display region of the cover lens, it is preferable that the diffuse reflectance is low from the viewpoint of design.

The hydroxyl value refers to the hydrogen required to neutralize the acetic acid bonded to the hydroxyl group when acetylating 1 g of (A) resin containing hydroxyl or acid groups according to Japanese Industrial Standards (JIS) K0070 (1992) The mg number of potassium oxide (unit: mgKOH/g). The acid value refers to the number of mg of potassium hydroxide required to neutralize (A) 1 g of hydroxyl or acid group-containing resin according to JIS K0070 (1992) (unit: mgKOH/g).

(A) The weight average molecular weight (Mw) of the resin containing a hydroxyl group or an acid group is preferably 500 or more and 150,000 or less. From the viewpoint of the reliability of the colored film, the weight average molecular weight is preferably from 5,000 to 150,000, more preferably from 10,000 to 150,000. Here, the weight average molecular weight (Mw) refers to a value converted using a calibration curve based on standard polystyrene after analysis by gel permeation chromatography using tetrahydrofuran as a carrier.

(A) As a hydroxyl group or an acid group which the resin containing a hydroxyl group or an acid group has, a hydroxyl group, a carboxyl group, a carboxylic acid anhydride group, a sulfonic acid group, a phosphoric acid group etc. are mentioned. Two or more of these may be contained. Among these, a hydroxyl group or a carboxyl group is particularly preferable from the viewpoint of the adhesiveness or low-temperature curability after the reliability test of the coating film.

From the viewpoint of the storage stability of the pigment dispersion liquid, the curability of the colored resin composition, and the adhesiveness of the obtained colored film to the substrate, (A) contains a hydroxyl group or an acid The content of the base resin is preferably from 10% by mass to 99% by mass, more preferably from 25% by mass to 85% by mass. Here, the term "solid content" refers to components other than the solvent among the components contained in the composition. The solid content contains (A) hydroxyl or acid group-containing resin, (B) coloring material, (C) dispersant, (D) blocked isocyanate, and other additives. Furthermore, the curability of the colored resin composition and the adhesiveness of the colored film to the substrate are also affected by the content of (D) blocked isocyanate described later.

As (B) a coloring material, an organic pigment, an inorganic pigment, or a dye is mentioned, for example. In order to improve the heat resistance, reliability, and light resistance of the colored film, an organic pigment or an inorganic pigment is preferable.

Examples of organic pigments include: diketopyrrolopyrrole-based pigments; azo-based pigments such as azo, disazo, and polyazo; phthalocyanine-based pigments such as copper phthalocyanine, copper halide phthalocyanine, and metal-free phthalocyanine. ; Aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, violanthrone ) and other anthraquinone pigments; quinacridone pigments; dioxazine pigments; Quinophthalone pigments; threne pigments; metal complex pigments, etc.

Examples of inorganic pigments include titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitating barium sulfate, white carbon black, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, Red lead, molybdenum red, molybdenum orange, chrome vermilion, chrome yellow, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, chrome green, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine blue, dark blue, cobalt Blue, sky blue (cerulean blue), cobalt silica blue, cobalt zinc silica blue, manganese violet, cobalt violet, etc.

Examples of dyes include azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigo dyes, carbonium dyes, phthalocyanine dyes, methine dyes, and polymethine dyes.

As a black coloring material, a black organic pigment, a mixed color organic pigment, an inorganic pigment, etc. are mentioned, for example. As a black organic pigment, carbon black, perylene black, aniline black, a benzofuranone type pigment, etc. are mentioned, for example. Examples of the mixed-color organic pigment include those obtained by mixing two or more pigments having colors such as red, blue, green, purple, yellow, magenta, and cyan, and turning them into pseudo-black. Examples of black inorganic pigments include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; oxides, composite oxides, sulfides, and nitrogen oxides of the metals. compounds, nitrogen oxides, etc.

Examples of white coloring materials include titanium dioxide, barium carbonate, zirconia, calcium carbonate, barium sulfate, alumina white, and silica.

These coloring materials of 2 or more types may be contained.

The (B) coloring material in the colored resin composition of the present invention is preferably in a finely dispersed and stabilized dispersion state. When the dispersion of the coloring material is not sufficient, coarse particles of the coloring material exist in the obtained colored film and density occurs in the film. Therefore, it is considered to be the adhesiveness of the colored film after the light resistance test or the high temperature and high humidity test. main reason for the decline. The average particle size of the coloring material in the colored resin composition is preferably from 30 nm to 200 nm, more preferably from 30 nm to 120 nm. As a method of setting the average particle size of the coloring material within the above range, it is preferable to use an acrylic dispersant having a basic group as a dispersant, and to stabilize and uniformly distribute the coloring material in a fine state without re-aggregating the coloring material in the resin. dispersion. More specifically, a method of micronizing the coloring material by a salt milling method, or a method of producing a colored resin composition by finely dispersing the coloring material by a bead mill described later, etc. are mentioned.

The content of the (B) coloring material in the colored resin composition of the present invention is preferably 1% by mass to 60% by mass relative to 100% by mass of the total solid content. By making content of (B) a coloring material 1 mass part or more, the visible light shielding property of the coloring film obtained can be improved. In addition, since the coloring material is a component that does not shrink when hardened, a large amount of the coloring material reduces film stress and improves adhesion. From this viewpoint, the content of the coloring material is more preferably 13% by mass or more. On the other hand, even if the content of the (B) coloring material is too large, the adhesiveness of the colored film deteriorates because the resin component responsible for the curing reaction decreases. Therefore, the (B) content of the coloring material is preferably at most 60% by mass, more preferably at most 48% by mass.

The (C) dispersant in the colored resin composition of the present invention is an acrylic dispersant having a basic group. The so-called dispersant refers to a dispersant that contains a coloring material affinity group that has a chemical bond or adsorption effect on the surface of the coloring material, and a solvent-friendly polymer chain or group. The acrylic dispersant refers to a dispersant having a main chain obtained by copolymerizing a monomer containing a (meth)acrylic group. The main chain may be a capped copolymer, a random copolymer, or a copolymer having side chains such as a graft copolymer.

In the dispersion treatment described later, the dispersing agent exerts the following effects: improve the wettability of the coloring material in the dispersion medium, promote the deagglomeration of the coloring material, and make the particle size and viscosity of the coloring material Stabilizes and further suppresses color separation during storage or coating of the colored resin composition.

啶基及三嗪基等。分散劑可具有一種或兩種以上的該些鹼性基。該些中，就對著色材的吸附力良好且分散性高的方面而言，較佳為含有三級胺基及四級銨鹽基中的至少一種的分散劑，尤佳為具有三級胺基及四級銨鹽基兩者的分散劑。於對著色材的吸附力良好的情況下，在高溫高濕試驗、耐光性試驗的過程中自著色材脫離，藉此於著色膜中游離的分散劑減少，因此認為耐光性試驗、高溫高濕試驗後的著色膜的密接性提高。 As the (C) dispersant in the colored resin composition of the present invention, an acrylic resin excellent in reliability such as light resistance and high-temperature and high-humidity resistance is selected. Furthermore, since (C) the dispersing agent has a basic group, the dispersing agent is adsorbed on the surface of the coloring material, and the coloring material is finely dispersed when the coloring material is dispersed, and the dispersion state is stabilized by the steric barrier between the dispersing agents, thereby It has the effect of inhibiting viscosity increase or re-agglomeration over time. Examples of basic groups include: primary amino group, secondary amino group, tertiary amino group, quaternary ammonium group, amide group, imine group, imidazoline group, pyrrolyl group, imidazolyl group, benzimidazole group Base, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyrrolidinyl, piperidinyl, piperazinyl, indolyl, indolinyl, purinyl, quinolinyl, isoquinolinyl,

Pyridyl and triazinyl, etc. The dispersant may have one kind or two or more kinds of these basic groups. Among these, a dispersant containing at least one of a tertiary amine group and a quaternary ammonium salt group is preferable in terms of good adsorption force to the coloring material and high dispersibility, and a dispersant having a tertiary amine group is particularly preferable. Dispersants for both base and quaternary ammonium base. When the adsorption force to the coloring material is good, it will detach from the coloring material during the high temperature and high humidity test and the light fastness test, thereby reducing the free dispersant in the colored film. Therefore, it is considered that the light fastness test, high temperature and high humidity The adhesiveness of the colored film after the test was improved.

(C) When the amine value of the dispersant is too low, the adsorption to the coloring material becomes insufficient, and when the amine value is too high, the storage stability of the colored resin composition decreases. Therefore, the amine value is preferably not less than 1 mgKOH/g and not more than 200 mgKOH/g, more preferably not less than 20 mgKOH/g and not more than 150 mgKOH/g. From the viewpoint of the reliability of the colored film, the weight average molecular weight (Mw) is preferably from 500 to 150,000, more preferably from 5,000 to 150,000. It should be noted that the amine value in the present invention means the number of mg of KOH equivalent to the acid required to neutralize 1 g of the dispersant.

Examples of the acrylic dispersant having a basic group include: DISPERBYK (registered trademark)-112, 116, 151, 155, 156, 187, 190, 191, 194N, 199, 2000, 2001, 2006, 2008, 2009, 2010, 2012, 2013, 2015, 2020, 2022, 2025, 2050, 2055, 2070, DISPERBYK (registered trademark) LPN-6919, LPN-21116, LPN- 22102 (all of the above are manufactured by BYK-Chemie). Among these, examples of acrylic dispersants containing at least one of a tertiary amine group and a quaternary ammonium salt group include: DISPERBYK (registered trademark)-187, 190, 191, 194N , 199, 2000, 2001, 2006, 2009, 2010, 2012, 2013, 2015, 2022, 2025, 2050, 2055, DISPERBYK (registered trademark) LPN-6919, LPN-21116, as three As for the acrylic dispersant of both a quaternary amine and a quaternary ammonium salt, DISPERBYK (registered trademark) LPN-21116 is mentioned, for example.

From the viewpoint of improving dispersion stability, the content of the (C) dispersant is preferably at least 5 parts by mass, more preferably at least 10 parts by mass, based on 100 parts by mass of the (B) coloring material. On the other hand, the content of the dispersant is preferably at most 100 parts by mass, more preferably at most 60 parts by mass, relative to 100 parts by mass of the coloring material, from the viewpoint of improving the adhesiveness or reliability of the colored film.

(D) Blocked isocyanate is a compound having two or more isocyanate groups blocked by a blocking agent. The blocking agent is dissociated by heating and the isocyanate group is regenerated. Therefore, the pot life of the blocked isocyanate is long, and the viscosity stability of the ink containing it is excellent. In the colored resin composition of the present invention, blocked isocyanate is used as a hardening agent. Blocked isocyanates regenerate isocyanate groups by dissociating (deprotecting) the blocking agent due to heating at lower temperatures. The ink hardens by thermal reaction of the regenerated isocyanate group with the hydroxyl or acid groups of (A) hydroxyl or acid group-containing resin.

The type of isocyanate is not particularly limited, and includes aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, dimer or trimer obtained by modification of diisocyanate, and terminal isocyanate group-containing compound Wait. These may be used individually or in combination. Examples of aromatic diisocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, Isocyanate, dianisidine diisocyanate, etc. Examples of aliphatic diisocyanates include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, and 1,6-hexamethylene diisocyanate (1,6-Hexamethylene Diisocyanate). (HMDI below), 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, etc. Examples of alicyclic diisocyanates include lysine diisocyanate, isophorone diisocyanate (IPDI hereinafter), 1,3-bis(isocyanatomethyl)-cyclohexane , 4,4'-dicyclohexylmethane diisocyanate, etc. Furthermore, a dimer or a trimer obtained by modification of these diisocyanates is mentioned. As a modification method, biuretization, isocyanuration, etc. are mentioned. Alternatively, those obtained by reacting the diisocyanate compound or polyisocyanate compound with an active hydrogen compound such as ethylene glycol, propylene glycol, trimethylolpropane, ethanolamine, polyester polyol, polyether polyol, polyamide, etc. Compounds containing terminal isocyanate groups, etc.

Examples of the blocking agent include known blocking agents such as phenol, methyl ethyl ketone oxime, and sodium bisulfite. In the case of selecting polycarbonate, polyethylene terephthalate (Polyethylene Terephthalate, PET) film and other resins as the substrate, it is better to use a blocking agent that dissociates at a lower temperature and releases the isocyanate group. terminal isocyanate.

An active methylene compound or a pyrazole compound is mentioned as such a terminal blocking agent which can dissociate at lower temperature. Examples of active methylene compounds include: Meldrum's acid, dialkyl malonate, alkyl acetylacetate, 2-acetylacetyloxyethyl methacrylate, acetylacetone , Ethyl cyanoacetate, etc. Examples of pyrazole compounds include pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3, 5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, 3-methyl-5-phenylpyrazole, etc. Among them, diethyl malonate, 3,5-dimethylpyrazole, and the like are preferable.

Blocked isocyanate is available as a commercial item. For example, Coronate (Coronate) (registered trademark) AP Stabil (Stable) M, Cronaide (Coronate) (registered trademark) 2503, 2515, 2507, 2513, 2555, Milionide (Millionate) MS-50 (the above are manufactured by Nippon Polyurethane Industry Co., Ltd.), Duranate (Duranate) 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF- K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (manufactured by Asahi Kasei Chemical Co., Ltd.), Desmodur BL1100, BL1265 MPA/X, BL3575/1, BL3272MPA , BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN, PL340, PL350, Sumidur (registered trademark) BL3175 (the above are manufactured by Sumika Bayer Polyurethane Co., Ltd.)

The contents of (A) hydroxyl group or acid group-containing resin and (D) blocked isocyanate are preferably selected so that each functional group thereof is consumed after curing. For example, if the mass of (A) hydroxyl or acid group-containing resin is set to 100 mass parts, the content of (D) blocked isocyanate is preferably 1 mass part to 300 mass parts, more preferably 5 mass parts to 150 mass parts , and more preferably 10 to 100 parts by mass. When the content of the blocked isocyanate is within these ranges, the effect of being able to efficiently harden the hydroxyl group- or acid group-containing resin is obtained.

It is preferable that the colored resin composition of this invention further contains (E) organic solvent from the point which can improve applicability. (E) The organic solvent has the function of uniformly dissolving or dispersing (A) hydroxyl or acid group-containing resin, (B) coloring material, (C) dispersant, (D) blocked isocyanate, and the like. (E) The organic solvent is preferably a compound having a boiling point of 110° C. to 250° C. under atmospheric pressure. The colored resin composition of the present invention can be applied by a printing method such as a spin coater, a slit coater, screen printing, inkjet, gravure printing, or a bar coater. Therefore, if the boiling point is less than 110°C, then The drying speed of the organic solvent is fast, and the uniformity of the coating is prone to failure. On the other hand, when the boiling point exceeds 250° C., the organic solvent may remain in the obtained colored film, and the chemical resistance of the colored film may deteriorate.

Examples of (E) organic solvents include ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, alcohols, and the like.

Examples of ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol Alcohol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono -n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl- n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Examples of acetates include butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate. , Ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, cyclohexanol acetate, Propylene Glycol Diacetate, Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monoethyl Ether Acetate (hereinafter referred to as "PGMEA": boiling point 146.4°C), Dipropylene Glycol Monoethyl Ether Acetate, 3-Methyl Ether Acetate Oxy-3-methyl-1-butyl acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate Esters etc. Examples of esters include: lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, 2-hydroxy-3 -methyl butyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate , 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate , n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetylacetate Esters, ethyl acetoacetate, ethyl 2-oxobutyrate, etc. As ketones, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone etc. are mentioned, for example. As aromatic hydrocarbons, toluene, xylene, etc. are mentioned, for example. As amides, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. are mentioned, for example. Examples of alcohols include butanol, isobutanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, and 3-methyl-3-methoxybutanol , diacetone alcohol, etc. Two or more of these may be contained.

Among these, acetates are preferable in order to further stabilize the dispersion of the coloring material. (E) The content of the acetates in the organic solvent is preferably from 50% by mass to 100% by mass, more preferably from 70% by mass to 100% by mass.

When coating a colored resin composition on a substrate to form a colored film, coating with a die coating device has gradually become the mainstream as the size of the substrate increases. On the other hand, when forming a colored film as a decoration for cover lenses, or as a decorative film for shielding near-infrared sensors and near-infrared cameras, it is necessary to form a colored film on a small piece of glass, preferably using a screen printing device Or coating by inkjet device. It is preferable to contain two or more kinds of (E) organic solvents from the viewpoint of achieving better volatility or drying properties in coating with these die coating devices, screen printing devices, and inkjet devices. . From the viewpoint of uniform film thickness of the coating film obtained from the colored resin composition of the present invention, improvement of surface smoothness and adhesiveness, viewpoint of suppression of dry foreign matter in nozzles of die coating devices and inkjet devices, and screen printing From the viewpoint of the continuous printability of the printing device, it is preferable to contain 3% by mass to 90% by mass of an organic solvent having a boiling point of 150°C to 250°C in the (E) organic solvent, more preferably 10% by mass to 75% by mass. quality%.

From the viewpoint of uniformity of film thickness of the coating film in the coating step, the content of (E) organic solvent in the colored resin composition of the present invention is preferably at least 50% by mass of the entire composition, more preferably More than 70% by mass. On the other hand, from the viewpoint of suppressing pigment sedimentation, the content of the (E) organic solvent is preferably at most 95% by mass of the entire composition, more preferably at most 90% by mass.

The colored resin composition of the present invention may also contain a leveling agent. By containing a leveling agent, coatability or the surface smoothness of a colored film can be improved. Examples of the leveling agent include anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; cationic surfactants such as stearylamine acetate and lauryl trimethylammonium chloride. ; Lauryl dimethylamine oxide, lauryl carboxymethyl hydroxyethyl imidazolium betaine and other amphoteric surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearyl Non-ionic surfactants such as acid esters; silicone-based surfactants with polydimethylsiloxane as the main skeleton; fluorine-based surfactants, etc. Two or more of these may be contained. Examples of commercially available surfactants include "BYK (registered trademark)" 302, 333, 3550, and 392 (all of which are manufactured by BYK-Chemie).

As a method for producing the colored resin composition of the present invention, for example, the following method is preferred: by using a disperser, the resin containing (A) hydroxyl group or acid group, (B) coloring material, (C) dispersant and ( E) Disperse the resin solution in an organic solvent, prepare a coloring material dispersion with a high concentration of coloring material in advance, and then add (A) resin containing hydroxyl or acid groups or (D) blocked isocyanate, and if necessary Other ingredients such as surfactants. Filtration of the obtained colored resin composition may be performed as needed.

As a disperser used for a dispersion process, a ball mill, a bead mill, a sand grinder, a three-roll mill, a high-speed impact mill, etc. are mentioned, for example. Among these, a bead mill is preferable for efficient dispersion and microdispersion. As a bead mill, a biconical ball mill (Co-Ball Mill), a basket mill (Basket Mill), a pin mill (Pin Mill), and a Dyno mill (Dyno-Mill) are mentioned, for example. Examples of the beads of the bead mill include titanium dioxide beads, zirconia beads, and zircon beads.

In the manufacturing method of the colored resin composition of this invention, it is preferable to carry out dispersion|distribution process in multiple stages by a bead mill. For example, it is preferable to disperse by a bead mill using beads having an average bead diameter of 0.1 mmΦ or less after the dispersion treatment is performed by a bead mill using beads having an average bead diameter larger than 0.1 mmΦ. deal with. The coloring material with a large crystallite size can be efficiently pulverized by performing dispersion treatment with a bead mill using beads having an average bead diameter larger than 0.1 mmΦ. Afterwards, the dispersion treatment is carried out by a bead mill using fine beads with an average bead diameter of 0.1 mmΦ or less, thereby reducing the energy applied to the coloring material, and micronizing while suppressing the surface activity of the coloring material. dispersion. Thereby, re-agglomeration of the coloring material in the colored resin composition can be suppressed, and the coloring material can be dispersed more uniformly and finely. In this case, the bead mill preferably includes a separator (separator) based on a centrifugal separation method capable of separating fine beads and dispersion liquid. Here, the term "average bead diameter" refers to the number average value of the approximate circular diameters of beads. Specifically, the beads can be photographed with a magnification of 45 times by using a solid microscope, and the longest diameter and the shortest diameter are respectively measured for 100 randomly selected beads, and the average value is used as the approximate diameter of the circle, and the number average value is calculated. Thereby, the bead diameter was obtained.

A colored film can be obtained by curing the colored resin composition of the present invention. From the viewpoint of preventing light leakage in the backlight, the light-shielding property of the colored film formed in the non-display area of the display is preferably an optical density (OD) value of 4.0 or more, more preferably an OD value of 4.5 or more.

Next, a method of curing the colored resin composition of the present invention to form a decorative substrate will be described. By the following method, the colored resin composition is coated on the substrate and cured to form a colored film, thereby obtaining a decorative substrate including the substrate and the colored film.

Examples of substrates include: transparent glass substrates such as soda glass, alkali-free glass, and aluminosilicate glass; resin substrates such as polycarbonate resin and acrylic resin; PET films, cycloolefin polymer (Cycloolefin Polymer, COP) films, etc. Membrane substrates; silicon wafers, ceramics, gallium arsenic substrates, etc. Examples of coating methods include spin coating using a spinner, spray coating, die coating, roll coating, inkjet printing, screen printing, and gravure printing. The film thickness of the coating film can be appropriately selected according to the coating method and the like. Generally, the film thickness after drying is set to 1 μm to 150 μm.

The obtained coating film is dried to obtain a dried film. As a drying method, heat drying, air drying, reduced-pressure drying, infrared irradiation, etc. are mentioned, for example. As a heating and drying apparatus, an oven, a hot plate, etc. are mentioned, for example. The drying temperature is preferably from 50°C to 150°C, and the drying time is preferably from 1 minute to several hours. This drying step can be expected to flatten the coating film by leveling or suppress foreign matter adhesion, etc., but this drying step is not necessarily required, and a colored film can be obtained only by heat treatment described later.

A colored film can be obtained by heat-treating (post-baking) the obtained coating film to harden it. The heat treatment can be performed in any of air, nitrogen atmosphere, and vacuum state. The heating temperature is preferably from 70°C to 300°C, particularly preferably from 80°C to 180°C. When the base material is a resin, the heating temperature can be selected according to the heat-resistant temperature of the base material. For example, when the base material is polycarbonate, the heating temperature is preferably 80°C to 120°C. The heating time is preferably from 0.25 hours to 5 hours. In the heat treatment, the heating temperature may be changed continuously or stepwise.

A decorative substrate including a substrate and a colored film containing a cured product of the colored resin composition of the present invention can be preferably used as a decorative substrate in a display terminal such as a smartphone or a tablet personal computer (PC) or a vehicle-mounted display, Near-infrared sensors for driver monitoring or gesture sensors in vehicle-mounted displays or instrumentation, decorative substrates for shielding near-infrared cameras, decorative films for hiding LiDAR sensors, etc. In addition, the colored film containing the cured product of the colored resin composition of the present invention can be suitably used for a light-shielding film such as a black matrix of a color filter included in a liquid crystal display device or the like, and an organic electroluminescence (EL) display. Internal colored partitions, etc. [Example]

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, the aspect of this invention is not limited to these.

＜Evaluation method＞ [closeness] About the colored film obtained by each Example and the comparative example, adhesiveness was evaluated based on JIS "K5600-5-6 (establishment date=1999/04/20)". Specifically, 11 vertical and horizontal parallel straight lines perpendicular to each other were drawn at intervals of 1 mm so as to reach the bottom of the substrate using a dicing knife on the colored film, and 100 grids of 1 mm×1 mm were produced. Stick cellophane adhesive tape (width = 18 mm, adhesion = 3.7 N/10 mm) on the surface of the cut colored film, wipe it with an eraser (JIS S6050 qualified product) to make the tape and the colored film tightly bonded, and hold the While holding the tape at right angles to the board at one end, the tape is instantly peeled off from the coloring film. At this time, the ratio of the peeled colored film was evaluated by visually confirming the number of grids of the colored film remaining without peeling from the substrate among the grids of 100 colored films. The adhesiveness of the colored film was judged as follows from the delamination area of the grid, and 4 or more was set as the pass. 5: Stripped area = 0% 4: Peeling area = <5% 3: Stripping area=5%～14% 2: Stripping area=15%～34% 1: Stripping area=35%～64% 0: peeled area = 65% to 100%.

[Measurement of viscosity] For the colored resin composition immediately after preparation and after 30°C/1 week, respectively, use an E-type viscometer ("Viscometer (VISCOMETER) TV-25" manufactured by Toki Sangyo Co., Ltd.) to measure the temperature at 25°C. viscosity. Based on the ratio (b)/(a) when the viscosity immediately after preparation is set as (a) and the viscosity after 30°C/1 week is set as (b), the coloring resin composition is determined as follows Viscosity stability at normal temperature, A and B were set as pass. A is the best and D is the worst. A: (b)/(a)≦1.1 B: 1.1<(b)/(a)≦1.5 C: 1.5<(b)/(a)≦2.0 D: 2.0<(b)/(a).

[high temperature and high humidity resistance] Using PC-242HS-E manufactured by Hirayama Seisakusho Co., Ltd., the coloring films obtained in Examples and Comparative Examples were treated for 24 hours at 121°C, 2 atmospheres, and 100% humidity, and then the above-mentioned [adhesiveness] was tested. Evaluation.

[Light resistance] Q-SUN xenon tester Xe-3 manufactured by Q-Lab Corporation was used, and Xe lamp X-1800 was used as the light source, and the brightness at a wavelength of 420 nm was ^1.2 W/m2. After the colored films obtained in Examples and Comparative Examples were irradiated with ultraviolet rays for 300 hours, the evaluation of the above-mentioned [adhesiveness] was performed.

[Average particle size of coloring material] The temperature of the dynamic light scattering particle size distribution meter (UPA-EX150 manufactured by MicrotracBEL) is set at 20°C ± 1°C, and the coloring material dispersion liquid or the coloring resin composition is propylene glycol monomethyl ether What was obtained by diluting acetate 400 times was measured, and the measured value (D50) obtained was made into the average particle diameter of a coloring material particle.

[diffuse reflection] For the colored films obtained by each of the Examples and Comparative Examples, a spectrophotometer (CM-2600d; Konica Minolta Co., Ltd.) calibrated with a white calibration plate (CM-A145; manufactured by Konica Minolta Co., Ltd.) was used. Manufactured by Konica Minolta (Konica Minolta Co., Ltd.), measuring the light incident from the transparent substrate side under the measurement conditions of standard light source D65 (color temperature 6504K), field angle 2° (CIE1976), atmospheric pressure, and 20°C Diffuse chromaticity (excluding Specular Component Exclude (SCE)). As an index of the diffuse reflectance of the colored film, (L*) was evaluated. From the viewpoint of design, the colored film formed in the non-display region of the cover lens preferably has a low L*.

[SOLVENT RESISTANCE] About the colored film obtained by each Example and the comparative example, the film thickness was measured using the contact film thickness gauge Surfcom (Surfcom) 1400D (made by Tokyo Precision Co., Ltd.). Cotton white cloth (cannequin No. 3) sufficiently infiltrated with isopropyl alcohol as a test solvent was stacked as a friction member so as to be in contact with the colored film. A friction test (10 reciprocations) was performed under a load condition (300 g/cm ² ), and then the film thickness was measured again. The solvent resistance of the colored film was obtained from the change in film thickness of the colored film before and after the rubbing test by the following formula. Those close to 100% were good, and 80% or more were regarded as acceptable. Solvent resistance (%)=film thickness after friction test (μm)×100/film thickness before friction test (μm) The evaluation of solvent resistance is to quantitatively evaluate the degree of hardenability during low-temperature sintering.

(Synthesis Example 1 Synthesis of Resin (P-1) Containing Hydroxyl or Acid Group) 100 g of isopropanol was charged into a 1000 cc four-neck flask, kept at 80° C. in an oil bath, sealed with nitrogen, and stirred, while using a dropping funnel for 30 minutes to drop and mix the mixture as The monomer is 30 g of methyl methacrylate, 40 g of styrene, 30 g of methacrylic acid and 2 g of N,N-azobisisobutyronitrile as an initiator. Thereafter, after continuing the reaction for 4 hours, after adding 1 g of hydroquinone monomethyl ether, the temperature was returned to normal temperature, and the polymerization was completed. Next, after adding 100 g of isopropanol to this polymer solution, while keeping it at 75°C, 40 g of glycidyl methacrylate and 3 g of triethylbenzyl ammonium chloride were added and reacted. 3 hours. After the reaction, the obtained resin solution was reprecipitated with purified water, filtered and dried to obtain hydroxyl or acid group-containing Resin (P-1). In addition, the hydroxyl value of a resin is measured according to JIS K0070 (1992), and the number of mg of potassium hydroxide required to neutralize the acetic acid bonded to a hydroxyl group when 1 g of resin is acetylated is measured. Acid value of resin The mg of potassium hydroxide required to neutralize 1 g of resin was measured according to JIS K0070 (1992). The weight average molecular weight was measured in terms of polystyrene using a gel permeation chromatograph (GPC) "HLC-8220GPC" (a test device manufactured by Tosoh Co., Ltd.) using tetrahydrofuran as a carrier.

(Synthesis Example 2 Synthesis of Hydroxyl or Acid Group-Containing Resin (P-2)) 100 g of isopropanol was charged into a 1000 cc four-neck flask, kept at 80° C. in an oil bath, sealed with nitrogen, and stirred, while using a dropping funnel for 30 minutes to drop and mix the mixture as Monomer 25 g of methyl methacrylate, 52 g of styrene, 33 g of 2-hydroxyethyl methacrylate and 2 g of N,N-azobisisobutyronitrile as an initiator. Thereafter, after continuing the reaction for 4 hours, after adding 1 g of hydroquinone monomethyl ether, the temperature was returned to normal temperature, and the polymerization was completed. After the reaction, the obtained resin solution was reprecipitated with purified water, filtered and dried to obtain hydroxyl or acid group-containing Resin (P-2).

(Synthesis Example 3 Synthesis of Hydroxyl or Acid Group-Containing Resin (P-3)) Except using 10 g of methyl methacrylate, 13 g of methacrylic acid, 21 g of styrene, and 72 g of 2-hydroxyethyl methacrylate as monomers, a weight average molecular weight of 12,500 and a hydroxyl value of 230 mgKOH/g, acid value 60 mgKOH/g resin containing hydroxyl or acid groups (P-3).

(Synthesis Example 4 Synthesis of Hydroxyl or Acid Group-Containing Resin (P-4)) Except for using 44 g of methyl methacrylate, 14 g of methacrylic acid, and 42 g of styrene as monomers, a weight average molecular weight of 14,000, a hydroxyl value of 0 mgKOH/g, and an acid value of 70 mgKOH/g were obtained in the same manner as in Synthesis Example 2. Resins containing hydroxyl or acid groups (P-4).

(Synthesis Example 5 Synthesis of Hydroxyl or Acid Group-Containing Resin (P-5)) Except for using 43 g of methyl methacrylate, 42 g of styrene, and 23 g of 2-hydroxyethyl methacrylate as monomers, a weight-average molecular weight of 15,000, a hydroxyl value of 70 mgKOH/g, and acid Hydroxyl or acid group-containing resin (P-5) with a value of 0 mgKOH/g.

(Synthesis Example 6 Synthesis of Hydroxyl or Acid Group-Containing Resin (P-6)) Except using 47 g of methyl methacrylate, 5 g of methacrylic acid, 42 g of styrene, and 10 g of 2-hydroxyethyl methacrylate as monomers, a weight-average molecular weight of 145,000 and a hydroxyl value of 30 mgKOH/g, acid value 40 mgKOH/g resin containing hydroxyl or acid groups (P-6). Table 1 shows the hydroxyl values and acid values of Synthesis Example 1 to Synthesis Example 6.

[Table 1] [Table 1] (A) Resins containing hydroxyl or acid groups Hydroxyl value (mgKOH/g) Acid value (mgKOH/g) Hydroxyl value + acid value (mgKOH/g) P-1 0 110 110 P-2 100 0 100 P-3 230 60 290 P-4 0 70 70 P-5 70 0 70 P-6 30 40 70

(Manufacture Example 1: Manufacture of red pigment PR177-1) Put 200 g of "Cromophtal (registered trademark) Red (Red) A3B" manufactured by BASF Co., Ltd., 2400 g of sodium chloride, and 400 g of diethylene glycol into the Kneading was carried out at 70° C. for 8 hours in a kneader (manufactured by Moriyama Seisakusho Co., Ltd., S-type kneader (trade name)). Next, the kneaded product was poured into about 10 L of warm water, heated to 40° C., and stirred for 1 hour with a high-speed mixer to form a slurry, then filtered, and washed with water to remove sodium chloride and Diethylene glycol was vacuum-dried at 80° C. for 24 hours to obtain a red pigment PR177-1.

(Manufacture Example 2 Blue Pigment PB15: Manufacture of 6-1) Add 200 g of "LIONOL (registered trademark) BULE ES" manufactured by Toyo Color Co., Ltd., 2400 g of sodium chloride, and 400 g of diethylene glycol The mixture was kneaded at 70° C. for 8 hours in a kneader (manufactured by Moriyama Seisakusho Co., Ltd., S-type kneader (trade name)). Next, the kneaded product was poured into about 10 L of warm water, heated to 40° C., and stirred for 1 hour with a high-speed mixer to form a slurry, then filtered, and washed with water to remove sodium chloride and Diethylene glycol was vacuum-dried at 80° C. for 24 hours to obtain a blue pigment PB15:6-1.

(Production example 3 Production of yellow pigment PY150-1) Put 200 g of "E-4GN" manufactured by Lanxess Co., Ltd., 2400 g of sodium chloride, and 400 g of diethylene glycol into a kneader (manufactured by Moriyama Seisakusho Co., Ltd., S-type kneader (trade name)), kneading at 70°C for 8 hours. Next, the kneaded product was poured into about 10 L of warm water, heated to 40° C., and stirred for 1 hour with a high-speed mixer to form a slurry, then filtered, and washed with water to remove sodium chloride and Diethylene glycol was vacuum-dried at 80° C. for 24 hours to obtain a yellow pigment PY150-1.

(Production Example 4 Production of Bibenzofuran Pigment Bk-1) As a bisbenzofuran pigment, 200 g of "Irgaphor (registered trademark)" black (Black) S0100CF manufactured by BASF (BASF) Co., Ltd., 2400 g of sodium chloride and 400 g of dibenzofuran Ethylene glycol was charged into a kneader (manufactured by Moriyama Seisakusho Co., Ltd., S-type kneader (trade name)), and kneaded at 70° C. for 8 hours. Next, the kneaded product was poured into about 10 L of warm water, heated to 40° C., and stirred for 1 hour with a high-speed mixer to form a slurry, then filtered, and washed with water to remove sodium chloride and Diethylene glycol was vacuum-dried at 80° C. for 24 hours to obtain bisbenzofuran pigment Bk-1.

(Manufacture Example 5: Manufacture of Coloring Material Dispersion (DP-1)) 175 g of high-resistance carbon black TPK1227R (manufactured by Cabot Co., Ltd.), 179 g of propylene glycol monomethyl ether acetate (PGMEA) of the acrylic resin (P-1) obtained in Synthesis Example 1 35% by mass solution, 63 g of "DISPERBYK (registered trademark)" LP N6919 (BYK-Chemie) as an acrylic dispersant having a tertiary amino group as a basic group Produced by the company, propylene glycol monomethyl ether acetate 20% by mass solution) and 584 g of PGMEA were put into a tank, stirred for 20 minutes with a homomixer, and a predispersion liquid was obtained. The obtained pre-dispersion liquid was supplied to the Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd., which includes a centrifugal separator filled with 75% by volume of zirconia beads with a bead diameter of 0.30 mmΦ, at a rotation speed of 9 m /s to disperse for 20 minutes. Next, the liquid after the dispersion treatment was supplied to Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads with a bead diameter of 0.05 mmΦ, and dispersed at a rotation speed of 11 m/s for 90 minutes to obtain a solid content Coloring material dispersion DP-1 with a concentration of 25% by mass, coloring material/(resin + dispersant) (mass ratio) = 70/30.

(Manufacture Example 6: Manufacture of Coloring Material Dispersion (DP-2)) 175 g of high-resistance carbon black TPK1227R (manufactured by Cabot Co., Ltd.), 179 g of propylene glycol monomethyl ether acetate (PGMEA) of the acrylic resin (P-1) obtained in Synthesis Example 1 35% by mass solution, 31 g of "DISPERBYK (registered trademark)" LP N21116 (By Ke Chemical (BYK-Chemie) company make, propylene glycol monomethyl ether acetate 40 mass % solution) and 615 g of PGMEA were put into a tank, and it stirred for 20 minutes with the homomixer, and obtained the predispersion liquid. The obtained pre-dispersion liquid was supplied to the Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd., which includes a centrifugal separator filled with 75% by volume of zirconia beads with a bead diameter of 0.30 mmΦ, at a rotation speed of 9 m /s to disperse for 20 minutes. Next, the liquid after the dispersion treatment was supplied to Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads with a bead diameter of 0.05 mmΦ, and dispersed at a rotation speed of 11 m/s for 90 minutes to obtain a solid content Coloring material dispersion DP-2 with a concentration of 25% by mass, coloring material/(resin + dispersant) (mass ratio) = 70/30.

(Manufacture Example 7: Manufacture of Coloring Material Dispersion (DP-3)) 120 g of the red pigment PR177-1, 171 g of a 35% by mass solution of propylene glycol monomethyl ether acetate (PGMEA) of the acrylic resin (P-1) obtained in Synthesis Example 1, as "DISPERBYK (registered trademark)" LP N21116 (manufactured by BYK-Chemie) as an alkaline-based acrylic dispersant based on a quaternary ammonium base, propylene glycol monomethyl ether acetic acid 50 g of ester 40% by mass solution) and 659 g of PGMEA were put into a tank, and stirred for 20 minutes with a homomixer to obtain a predispersion liquid. The obtained pre-dispersion liquid was supplied to the Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd., which includes a centrifugal separator filled with 75% by volume of zirconia beads with a bead diameter of 0.50 mmΦ, at a rotation speed of 12 m /s to disperse for 20 minutes. Next, the liquid after the dispersion treatment was supplied to Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads with a bead diameter of 0.05 mmΦ, and dispersed at a rotation speed of 8 m/s for 90 minutes to obtain a solid content Coloring material dispersion DP-3 with a concentration of 20% by mass, coloring material/(resin + dispersant) (mass ratio) = 60/40.

(Manufacture Example 8: Manufacture of Coloring Material Dispersion (DP-4)) Except for using the blue pigment PB15:6-1 instead of the red pigment PR177-1, the solid content concentration was 20% by mass, and the coloring material/(resin+dispersant) (mass ratio)=60/40 was obtained in the same manner as in Production Example 7. Coloring material dispersion liquid DP-4.

(Manufacture Example 9: Manufacture of Coloring Material Dispersion (DP-5)) Except for using the yellow pigment PY150-1 instead of the red pigment PR177-1, a coloring material having a solid content concentration of 20% by mass and a coloring material/(resin + dispersant) (mass ratio) = 60/40 was obtained in the same manner as in Production Example 7. Dispersion DP-5.

(Manufacture Example 10 Manufacture of Coloring Material Dispersion (DP-6)) Except for using bisbenzofuranone-based pigment Bk-1 instead of red pigment PR177-1, solid content concentration of 20% by mass, coloring material/(resin + dispersant) (mass ratio) = 60 was obtained in the same manner as in Production Example 7 /40 coloring material dispersion DP-6.

(Manufacture Example 11 Manufacture of Coloring Material Dispersion (DP-7)) 175 g of high-resistance carbon black TPK1227R (manufactured by Cabot Co., Ltd.), 35% by mass of propylene glycol monomethyl ether acetate (PGMEA) of the acrylic resin (P-1) obtained in Synthesis Example 1 Solution 179 g, "DISPERBYK (registered trademark)" LP N21116 (BYK- Chemie) Co., Ltd., 31 g of propylene glycol monomethyl ether acetate 40% by mass solution) and 615 g of PGMEA were put into a tank, and stirred for 20 minutes with a homomixer to obtain a predispersion liquid. The obtained pre-dispersion was supplied to a paint shaker (Toyo Seiki Seisakusho Co., Ltd.), dispersed for 3 hours using zirconia beads with a bead diameter of 1.0 mmΦ, and then filtered through a 5 μm filter. The coloring material dispersion DP-7 having a solid content concentration of 20% by mass and a coloring material/(resin+polymer dispersant) (mass ratio)=60/40 was obtained.

(Manufacture Example 12 Manufacture of Coloring Material Dispersion (DP-8)) 175 g of high-resistance carbon black TPK1227R (manufactured by Cabot Co., Ltd.), 35% by mass of propylene glycol monomethyl ether acetate (PGMEA) of the acrylic resin (P-1) obtained in Synthesis Example 1 Solution 179 g, "DISPERBYK (registered trademark)" 167 as a urethane-based dispersant (manufactured by BYK-Chemie, 52% by mass solution of butyl acetate) 24 g and 622 g of PGMEA were put into a tank, stirred for 20 minutes with a homomixer, and obtained a predispersion liquid. The obtained pre-dispersion liquid was supplied to the Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd., which includes a centrifugal separator filled with 75% by volume of zirconia beads with a bead diameter of 0.30 mmΦ, at a rotation speed of 9 m /s to disperse for 20 minutes. Next, the liquid after the dispersion treatment was supplied to Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads with a bead diameter of 0.05 mmΦ, and dispersed at a rotation speed of 11 m/s for 90 minutes to obtain a solid content Coloring material dispersion DP-8 with a concentration of 25% by mass, coloring material/(resin + dispersant) (mass ratio) = 70/30. Table 2 shows the compositions and dispersion conditions of Production Examples 5 to 12.

[Table 2] [Table 2]

(Example 1) Add 26.56 g of PGMEA 35% by mass solution of hydroxyl or acid group-containing resin (P-1) to 31.43 g of coloring material dispersion (DP-1), and 6.43 g of Oxime-based capping agent as the end-capping agent Coronate (registered trademark) BI-301 (manufactured by Tosoh Co., Ltd.), Solvesso (registered trademark) 100 (Exxon Chemical (Exxon Chemical Co., Ltd.) ) manufactured) 75% by mass solution), 0.20 g of PGMEA 10 of the silicone-based surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie) as a surfactant The mass % solution was dissolved in 36.98 g of PGMEA to obtain a colored resin composition PC-1 having a total solid concentration of 22 mass % and a coloring material content of 25 parts by mass relative to 100 parts by mass of the total solid content.

Using a spinner (1H-DS) manufactured by Mikasa Co., Ltd., the obtained colored resin composition PC-1 was coated on a polyester film (manufactured by Toray Co., Ltd., Lumirror ) (registered trademark) U48, film thickness: 100 μm) to form a coating film on the easy-adhesive layer. The coating film was heated and dried in an oven at 90° C. for 30 minutes to obtain colored film C-1. About this coloring film C-1, it evaluated by the said method. The results are shown in Table 4.

(Example 2) Colored resin composition PC-2 was obtained in the same manner as in Example 1 except that the coloring material dispersion (DP-2) was used instead of the coloring material dispersion (DP-1). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-2. The results are shown in Table 4.

(Example 3) Add 26.56 g of PGMEA 35% by mass solution of hydroxyl or acid group-containing resin (P-1) to 31.43 g of coloring material dispersion (DP-2), and 6.89 g of pyrazole-based capping agent as the capping agent. Duranate (registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd., PGMEA 70 mass % solution) of blocked isocyanate as a terminal agent, 0.20 g of silicone-based surfactant "Bi BYK (registered trademark)" 333 (manufactured by BYK-Chemie) PGMEA 10% by mass solution was dissolved in 34.91 g of PGMEA to obtain a total solid content concentration of 22% by mass, relative The content of the coloring material was 25 parts by mass of the colored resin composition PC-3 based on 100 parts by mass of the total solid content. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-3. The results are shown in Table 4.

(Example 4) Add 26.56 g of PGMEA 35% by mass solution of hydroxyl or acid group-containing resin (P-1) to 31.43 g of coloring material dispersion (DP-2), 8.04 g of active methylene as a capping agent Duranate (registered trademark) MF-K60B (manufactured by Asahi Kasei Co., Ltd., n-butyl acetate/n-butanol 60% by mass solution) as a blocking agent, 0.20 g of a silicone-based surfactant as a surfactant A solution obtained by dissolving a 10% by mass solution of PGMEA of the surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie) in 33.77 g of PGMEA to obtain a total solid content concentration 22% by mass, colored resin composition PC-4 having a coloring material content of 25 parts by mass relative to 100 parts by mass of the total solid content. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-4. The results are shown in Table 4.

(Example 5) Colored resin composition PC-5 was obtained like Example 3 except having used the hydroxyl group or acid group containing resin (P-2) instead of the hydroxyl group or acid group containing resin (P-1). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-5. The results are shown in Table 4.

(Example 6) Add 23.27 g of hydroxyl or acid group-containing PGMEA 35% by mass solution of resin (P-1), 6.67 g of Duranate (registered trademark) SBB-70P (Asahi Kasei Co., Ltd. )), 0.20 g of PGMEA 10% by mass solution of the silicone-based surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie) as a surfactant was dissolved in From the solution obtained in 24.03 g of PGMEA, a colored resin composition PC-6 having a total solid content concentration of 22 mass % and a coloring material content of 25 parts by mass relative to 100 parts by mass of the total solid content was obtained. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-6. The results are shown in Table 4.

(Example 7) Add 23.27 g of PGMEA 35% by mass solution of hydroxyl or acid group-containing resin (P-1) to 45.83 g of coloring material dispersion (DP-6), and 6.67 g of pyrazole-based capping agent as the capping agent. Duranate (registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.) of blocked isocyanate as a terminal agent, 0.20 g of silicone-based surfactant "BYK (registered trademark)" as a surfactant Trademark) "333 (manufactured by BYK-Chemie) PGMEA 10% by mass solution dissolved in 24.03 g of PGMEA to obtain a total solid concentration of 22% by mass, relative to the total solid content of 100% by mass The content of the coloring material is 25 parts by mass of the colored resin composition PC-7. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-7. The results are shown in Table 4.

(Example 8) Colored resin composition PC-8 was obtained in the same manner as in Example 3 except that the coloring material dispersion (DP-7) was used instead of the coloring material dispersion (DP-2). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-8. The results are shown in Table 4.

(Example 9) Add 33.52 g of PGMEA 35% by mass solution of hydroxyl or acid group-containing resin (P-1) to 18.86 g of coloring material dispersion (DP-2), and 7.90 g of pyrazole-based capping agent as the capping agent. Duranate (registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.) of blocked isocyanate as a terminal agent, 0.20 g of silicone-based surfactant "BYK (registered trademark)" as a surfactant Trademark) "333 (manufactured by BYK-Chemie) PGMEA 10% by mass solution dissolved in 39.52 g of PGMEA to obtain a total solid concentration of 22% by mass, relative to the total solid content of 100% by mass The content of the coloring material is 15 parts by mass of the colored resin composition PC-9. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-9. The results are shown in Table 4.

(Example 10) Add 12.64 g of PGMEA 35% by mass solution of hydroxyl or acid group-containing resin (P-1) to 56.57 g of coloring material dispersion (DP-2), and 4.87 g of pyrazole-based capping agent as the capping agent. Duranate (registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.) of blocked isocyanate as a terminal agent, 0.20 g of silicone-based surfactant "BYK (registered trademark)" as a surfactant Trademark) "333 (manufactured by BYK-Chemie) PGMEA 10% by mass solution dissolved in 25.71 g of PGMEA to obtain a total solid concentration of 22% by mass, relative to the total solid content of 100% by mass The content of the coloring material is 45 parts by mass of the colored resin composition PC-10. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-10. The results are shown in Table 4.

(Example 11) Add 37.00 g of PGMEA 35% by mass solution of hydroxyl or acid group-containing resin (P-1) to 12.57 g of coloring material dispersion (DP-2), and 8.41 g of pyrazole-based capping agent as the capping agent. Duranate (registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.) of blocked isocyanate as a terminal agent, 0.20 g of silicone-based surfactant "BYK (registered trademark)" as a surfactant Trademark) "333 (manufactured by BYK-Chemie) PGMEA 10% by mass solution dissolved in 41.82 g of PGMEA to obtain a total solid concentration of 22% by mass, relative to the total solid content of 100% by mass The content of the colored material in 10 parts is 10 parts by mass of the colored resin composition PC-11. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-11. The results are shown in Table 4.

(Example 12) Add 9.16 g of PGMEA 35% by mass solution of hydroxyl or acid group-containing resin (P-1) to 62.86 g of coloring material dispersion (DP-2), and 4.37 g of pyrazole-based capping agent as the capping agent. Duranate (registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.) of blocked isocyanate as a terminal agent, 0.20 g of silicone-based surfactant "BYK (registered trademark)" as a surfactant Trademark) "333 (manufactured by BYK-Chemie) PGMEA 10% by mass solution dissolved in 23.41 g of PGMEA to obtain a total solid concentration of 22% by mass, relative to the total solid content of 100% by mass The content of the coloring material is 50 parts by mass of the colored resin composition PC-12. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-12. The results are shown in Table 4.

(Example 13) Add 17.37 g of PGMEA 35% by mass solution of hydroxyl or acid group-containing resin (P-1) to 31.43 g of coloring material dispersion (DP-2), and 11.49 g of pyrazole-based capping agent as the capping agent. Duranate (registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.) of blocked isocyanate as a terminal agent, 0.20 g of silicone-based surfactant "BYK (registered trademark)" as a surfactant Trademark) "333 (manufactured by BYK-Chemie) PGMEA 10% by mass solution dissolved in 39.51 g of PGMEA to obtain a total solid concentration of 22% by mass, relative to the total solid content of 100% by mass The content of the coloring material is 25 parts by mass of the colored resin composition PC-13. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-13. The results are shown in Table 4.

(Example 14) Add 35.75 g of PGMEA 35% by mass solution of hydroxyl or acid group-containing resin (P-1) to 31.43 g of coloring material dispersion (DP-2), and 2.30 g of pyrazole-based capping agent as the capping agent. Duranate (registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.) of blocked isocyanate as a terminal agent, 0.20 g of silicone-based surfactant "BYK (registered trademark)" as a surfactant Trademark) "333 (manufactured by BYK-Chemie) PGMEA 10% by mass solution dissolved in 30.32 g of PGMEA to obtain a total solid concentration of 22% by mass, relative to the total solid content of 100% by mass The content of the coloring material is 25 parts by mass of the colored resin composition PC-14. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-14. The results are shown in Table 4.

(Example 15) Add 35.75 g of PGMEA 35% by mass solution of hydroxyl or acid group-containing resin (P-3) to 31.43 g of coloring material dispersion (DP-2), and 2.30 g of pyrazole-based capping agent as the capping agent. Duranate (registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.) of blocked isocyanate as a terminal agent, 0.20 g of silicone-based surfactant "BYK (registered trademark)" as a surfactant Trademark) "333 (manufactured by BYK-Chemie) PGMEA 10% by mass solution dissolved in 30.32 g of PGMEA to obtain a total solid concentration of 22% by mass, relative to the total solid content of 100% by mass The content of the coloring material is 25 parts by mass of the colored resin composition PC-15. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-15. The results are shown in Table 4. (Example 16) Add 35.75 g of PGMEA 35% by mass solution of hydroxyl or acid group-containing resin (P-4) to 31.43 g of coloring material dispersion (DP-2), and 2.30 g of pyrazole-based capping agent as the capping agent. Duranate (registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.) of blocked isocyanate as a terminal agent, 0.20 g of silicone-based surfactant "BYK (registered trademark)" as a surfactant Trademark) "333 (manufactured by BYK-Chemie) PGMEA 10% by mass solution dissolved in 30.32 g of PGMEA to obtain a total solid concentration of 22% by mass, relative to the total solid content of 100% by mass The content of the colored material is 25 parts by mass of the colored resin composition PC-16. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-16. The results are shown in Table 4. (Example 17) Add 35.75 g of PGMEA 35% by mass solution of hydroxyl or acid group-containing resin (P-5) to 31.43 g of coloring material dispersion (DP-2), and 2.30 g of pyrazole-based capping agent as the capping agent. Duranate (registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.) of blocked isocyanate as a terminal agent, 0.20 g of silicone-based surfactant "BYK (registered trademark)" as a surfactant Trademark) "333 (manufactured by BYK-Chemie) PGMEA 10% by mass solution dissolved in 30.32 g of PGMEA to obtain a total solid concentration of 22% by mass, relative to the total solid content of 100% by mass The content of the coloring material is 25 parts by mass of the colored resin composition PC-17. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-17. The results are shown in Table 4. (Example 18) Add 35.75 g of PGMEA 35% by mass solution of hydroxyl or acid group-containing resin (P-6) to 31.43 g of coloring material dispersion (DP-2), and 2.30 g of pyrazole-based capping agent as the capping agent. Duranate (registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.) of blocked isocyanate as a terminal agent, 0.20 g of silicone-based surfactant "BYK (registered trademark)" as a surfactant Trademark) "333 (manufactured by BYK-Chemie) PGMEA 10% by mass solution dissolved in 30.32 g of PGMEA to obtain a total solid concentration of 22% by mass, relative to the total solid content of 100% by mass The content of the colored material is 25 parts by mass of the colored resin composition PC-18. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-18. The results are shown in Table 4.

(comparative example 1) Colored resin composition PC-19 was obtained in the same manner as in Example 3 except that the coloring material dispersion (DP-8) was used instead of the coloring material dispersion (DP-2). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-19. The results are shown in Table 4.

(comparative example 2) Adding 26.56 g of PGMEA 35% by mass solution of hydroxyl or acid group-containing resin (P-1) to 31.43 g of coloring material dispersion (DP-2), replacing 4.83 g of epoxy resin with blocked isocyanate "Techmore" VG-3101L (manufactured by Printec Co., Ltd.), 0.20 g of silicone-based surfactant "BYK (registered trademark)" as a surfactant 333 (manufactured by BYK-Chemie) PGMEA 10 mass % solution dissolved in 36.98 g of PGMEA to obtain a coloring with a total solid content concentration of 22 mass % relative to 100 mass parts of the total solid content The content of the material is 25 parts by mass of the colored resin composition PC-20. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-20. The results are shown in Table 4.

[Table 3] [Table 3] Colored resin composition Colored resin composition (A) Resins containing hydroxyl or acid groups Coloring material dispersion (D) Blocked isocyanate epoxy resin (E) Organic solvents (B) Coloring material content ^*1 (D) Blocked isocyanate content ^{※ 2} Example 1 PC-1 P-1 DP-1 Coronate® BI-301 - PGMEA 25 parts by mass 43 parts by mass Example 2 PC-2 P-1 DP-2 Coronate® BI-301 - PGMEA 25 parts by mass 43 parts by mass Example 3 PC-3 P-1 DP-2 Duranate® SBB-70P - PGMEA 25 parts by mass 43 parts by mass Example 4 PC-4 P-1 DP-2 Duranate® MF-K60B - PGMEA 25 parts by mass 43 parts by mass Example 5 PC-5 P-2 DP-2 Duranate® SBB-70P - PGMEA 25 parts by mass 43 parts by mass Example 6 PC-6 P-1 DP-3:DP-4:DP-5=50:35:15 Duranate® SBB-70P - PGMEA 25 parts by mass 43 parts by mass Example 7 PC-7 P-1 DP-6 Duranate® SBB-70P - PGMEA 25 parts by mass 43 parts by mass Example 8 PC-8 P-1 DP-7 Duranate® SBB-70P - PGMEA 25 parts by mass 43 parts by mass Example 9 PC-9 P-1 DP-2 Duranate® SBB-70P - PGMEA 15 parts by mass 43 parts by mass Example 10 PC-10 P-1 DP-2 Duranate® SBB-70P - PGMEA 45 parts by mass 43 parts by mass Example 11 PC-11 P-1 DP-2 Duranate® SBB-70P - PGMEA 10 parts by mass 43 parts by mass Example 12 PC-12 P-1 DP-2 Duranate® SBB-70P - PGMEA 50 parts by mass 43 parts by mass Example 13 PC-13 P-1 DP-2 Duranate® SBB-70P - PGMEA 25 parts by mass 100 parts by mass Example 14 PC-14 P-1 DP-2 Duranate® SBB-70P - PGMEA 25 parts by mass 11 parts by mass Example 15 PC-15 P-3 DP-2 Duranate® SBB-70P - PGMEA 25 parts by mass 43 parts by mass Example 16 PC-16 P-4 DP-2 Duranate® SBB-70P - PGMEA 25 parts by mass 43 parts by mass Example 17 PC-17 P-5 DP-2 Duranate® SBB-70P - PGMEA 25 parts by mass 43 parts by mass Example 18 PC-18 P-6 DP-2 Duranate® SBB-70P - PGMEA 25 parts by mass 43 parts by mass Comparative example 1 PC-19 P-1 DP-8 Duranate® SBB-70P - PGMEA 25 parts by mass 43 parts by mass Comparative example 2 PC-20 P-1 DP-2 - VG3101L PGMEA 25 parts by mass 43 parts by mass *1: Parts by mass relative to 100 parts by mass of the total solid content *2: Parts by mass relative to 100 parts by mass of (A) hydroxyl or acid group-containing resin

[Table 4] [Table 4] Colored resin composition Evaluation Results of Colored Resin Compositions Evaluation results of colored film Average particle size (nm) (a) Initial viscosity (cP) (b) Viscosity over time (cP) (b)/(a) viscosity stability Closeness High temperature and high humidity resistance Lightfastness Diffuse reflection SCE L* Solvent resistance Example 1 PC-1 107 18.4 22.1 1.2 B 4 4 4 1.3 89% Example 2 PC-2 93 18.7 18.4 1.0 A 5 5 5 1.2 92% Example 3 PC-3 94 17.6 18.3 1.0 A 5 5 5 1.3 98% Example 4 PC-4 94 18.5 18.7 1.0 A 5 5 5 1.1 97% Example 5 PC-5 95 6.0 6.2 1.0 A 5 5 5 1.2 98% Example 6 PC-6 59 21.5 22.8 1.1 A 5 5 5 0.4 95% Example 7 PC-7 52 18.5 19.5 1.1 A 5 5 5 0.4 94% Example 8 PC-8 135 16.5 16.6 1.0 A 4 4 4 3.2 88% Example 9 PC-9 93 28.1 30.1 1.1 A 5 5 5 1.8 96% Example 10 PC-10 94 7.0 7.0 1.0 A 5 5 5 0.8 95% Example 11 PC-11 96 35.6 38.3 1.1 A 4 4 4 1.9 90% Example 12 PC-12 93 5.7 5.7 1.0 A 4 4 4 1.1 91% Example 13 PC-13 93 14.2 16.4 1.2 B 5 4 4 1.2 89% Example 14 PC-14 95 22.4 22.5 1.0 A 5 4 4 1.3 88% Example 15 PC-15 93 25.7 25.4 1.0 A 5 4 5 1.1 96% Example 16 PC-16 95 16.4 20.5 1.3 B 5 4 5 2.7 95% Example 17 PC-17 94 5.6 8.3 1.5 B 4 4 4 2.8 91% Example 18 PC-18 95 15.7 22.1 1.4 B 5 4 4 2.6 93% Comparative example 1 PC-19 141 16.9 26.2 1.6 C 3 2 3 3.1 78% Comparative example 2 PC-20 96 16.1 59.4 3.7 D. 4 4 3 1.2 79%

It can be seen that the colored resin compositions of Examples are excellent in viscosity stability and curability during low-temperature sintering, and have high adhesion after light resistance test and high-temperature and high-humidity test. On the other hand, it can be seen that the coloring resin composition of Comparative Example 1 has insufficient viscosity stability, and the adhesiveness after the adhesiveness and light resistance test, and the high-temperature and high-humidity test is low. It can also be seen that the hardenability at the time of low-temperature sintering is not sufficient. In addition, it was found that the colored resin composition of Comparative Example 2 was insufficient in viscosity stability and curability during low-temperature sintering. [industrial availability]

The colored resin composition of the present invention can be suitably used as a black decorative ink for forming a light-shielding film covering a non-display area of a lens in an on-vehicle display or the like.

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Claims (10)

A colored resin composition, containing (A) resin containing hydroxyl or acid groups, (B) coloring material, (C) dispersant and (D) blocked isocyanate, the (C) dispersant is Acrylic dispersant. The colored resin composition according to claim 1, wherein the (C) dispersant contains at least one of tertiary amine groups and quaternary ammonium groups. The colored resin composition according to any one of claim 1 to claim 2, wherein the average particle diameter of the (B) coloring material in the colored resin composition is 30 nm to 120 nm. The colored resin composition according to any one of claim 1 to claim 3, wherein the total of the acid value and hydroxyl value of the (A) hydroxyl or acid group-containing resin is 80 mgKOH/g to 300 mgKOH/g g. The colored resin composition according to any one of claim 1 to claim 4, wherein the (D) blocked isocyanate contains at least one blocking agent selected from active methylene compounds and pyrazole compounds. The colored resin composition according to any one of claim 1 to claim 5, wherein the (D) blocked isocyanate is Content is 5 mass parts or more and 150 mass parts or less. The colored resin composition according to any one of claim 1 to claim 6, wherein the content of the (B) coloring material is 13% by mass to 48% by mass in 100% by mass of the total solid content. The colored resin composition according to any one of claims 1 to 7, further comprising (E) an organic solvent. A colored film comprising a cured product of the colored resin composition according to any one of claim 1 to claim 8. A decorative substrate, comprising a substrate and the colored film as claimed in Claim 9.