Colored resin composition, colored film, decorative substrate

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

Technical Field

[0001] The present invention relates to a colored resin composition, a colored film, and a decorated substrate.

Background Art

[0002] In touch panels of various information terminals such as smartphones and in-vehicle displays, a light-shielding film is formed in a non-display area of a cover lens located on the outermost layer as viewed from the user side, and the light-shielding film serves to conceal electrodes such as the routing wiring of a touch sensor.

[0003] In-vehicle displays and smartwatches are required to have reliability such that their operability and designability do not change even under ultraviolet irradiation of sunlight or in a high-temperature and high-humidity environment. For the light-shielding film of the cover lens, it is required that the adhesion does not decrease in such an environment.

[0004] In particular, in the case of in-vehicle displays, the material of the cover lens may be a resin such as polycarbonate. As a method for forming a light-shielding film on the resin, there are a method of directly printing ink on the resin by screen printing, inkjet printing, gravure printing, etc., and a method of manufacturing a cover lens by in-mold molding of a decorative film. In any method, since the heat resistance of the base material is lower than that of glass, an ink that can be cured by low-temperature baking at 80 to 120°C is required. Also, in these printing methods, it is required that the viscosity does not change at room temperature from the viewpoints of continuous printability and film thickness reproducibility.

[0005] Therefore, for example, in Patent Document 1, an inkjet printing ink containing a carboxyl group-containing binder polymer having a weight average molecular weight of 20,00 to 300,000 and a curing agent containing a blocked isocyanate and an epoxy resin has been studied. Also, in Patent Document 2, an inkjet printing ink containing a glycol ether-based solvent and an acetate-based solvent and containing an acrylic resin having a hydroxyl group and a low-temperature dissociation block-type isocyanate has been studied as an ink that can be printed on a non-heat-resistant non-absorbent medium and can be cured at a low temperature. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2018 / 155500 [Patent Document 2] Japanese Patent Publication No. 2016-138229 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, while the ink described in Patent Document 1 can maintain high adhesion even after various reliability tests by using both blocked isocyanate and epoxy resin, its viscosity stability was insufficient because the epoxy resin reacts with the carboxyl groups of the polymer, causing changes in film thickness and printing accuracy when used for long-term printing. Furthermore, while the ink described in Patent Document 2 can be cured at low temperatures and has excellent viscosity stability, its adhesion deteriorates after rigorous reliability tests for automotive standards, and its properties are insufficient from the standpoint of light resistance and high temperature and humidity resistance.

[0008] Therefore, the present invention aims to provide a colored resin composition that can be cured at low temperatures, has excellent viscosity stability at room temperature, and maintains high adhesion even after lightfastness tests and high-temperature, high-humidity tests. [Means for solving the problem]

[0009] As a result of diligent research, the inventors of the present invention have found that the above problems can be solved by incorporating a hydroxyl group or acid group-containing resin, a coloring agent, a dispersant, and a blocked isocyanate into the colored resin composition, and by applying an acrylic dispersant having a basic group as the dispersant, thereby completing the present invention.

[0010] In other words, the objective of the present invention is achieved primarily by the following configuration. A colored resin composition comprising (A) a hydroxyl group or acid group-containing resin, (B) a coloring agent, (C) a dispersant, and (D) a blocked isocyanate, wherein (C) the dispersant is an acrylic dispersant having a basic group. [Effects of the Invention]

[0011] The colored resin composition of the present invention can be cured at low temperatures, has excellent viscosity stability at room temperature, and can produce a colored film that maintains high adhesion even after light resistance tests and high temperature and high humidity tests. [Modes for carrying out the invention]

[0012] The present invention will be described in more detail below.

[0013] The colored resin composition of the present invention contains (A) a hydroxyl group or acid group-containing resin, (B) a coloring agent, (C) a dispersant, and (D) a blocked isocyanate. (A) The hydroxyl group or acid group-containing resin acts as a binder in the composition. (B) The coloring agent has the effect of blocking visible light. (C) The dispersant has the effect of uniformly dispersing the coloring agent and preventing re-aggregation. (D) The blocked isocyanate has the effect of reacting with the hydroxyl groups or acid groups contained in the resin only during heating and firing.

[0014] The present invention is characterized in that the (C) dispersant is an acrylic dispersant having a basic group. Acrylic dispersants have excellent reliability in terms of light resistance, high temperature and high humidity resistance, etc. Furthermore, because the dispersant has a basic group, the dispersant is adsorbed onto the surface of the colorant, finely disperses the colorant during dispersion, stabilizes the dispersion state due to steric hindrance between the dispersants, and has the effect of suppressing thickening and re-aggregation over time. In addition, (D) the blocked isocyanate is unreactive at room temperature due to the function of the blocking agent and is reactive only when heated, so the viscosity stability of the colored resin composition can be kept good, and by appropriately selecting the blocking agent, the blocking agent can dissociate at low temperatures and react with hydroxyl groups or acid groups.

[0015] (A) Hydroxyl group or acid group-containing resin is a resin having a hydroxyl group or acid group. (A) Examples of hydroxyl group or acid group-containing resins include acrylic resin, cardo resin, siloxane resin, polyimide resin, polyimide precursor, polyurethane resin, polyester resin, and vinyl chloride resin. Two or more of these may be included. Among these, acrylic resin, polyurethane resin, or polyester resin is preferred from the viewpoint of storage stability of the colored resin composition and adhesion and reliability of the colored film, and acrylic resin is particularly preferred.

[0016] (A) The hydroxyl group or acid group-containing resin is preferably such that the hydroxyl value or acid value is 10 mg KOH / g or higher from the viewpoint of viscosity stability of the colored resin composition, curing speed, adhesion of the colored film, and reliability of the colored film. The hydroxyl value is preferably 20 to 300 mg KOH / g, and more preferably 90 to 250 mg KOH / g. The acid value is preferably 20 to 300 mg KOH / g, and more preferably 60 to 150 mg KOH / g. The sum of the acid value and hydroxyl value is preferably 80 to 300 mg KOH / g, and more preferably 100 to 300 mg KOH / g. If the sum of the acid value and hydroxyl value is less than 80 mg KOH / g, the number of functional groups that react with (D) blocked isocyanate decreases, which may lead to a decrease in curing speed and deterioration of adhesion after various reliability tests. Furthermore, when the sum of the acid value and hydroxyl value is less than 80 mgKOH / g, a decrease in viscosity stability and an increase in the diffuse reflectance of the resulting colored film are observed. This decrease in viscosity stability and increase in the diffuse reflectance of the colored film are thought to be caused by a deterioration in the compatibility between (A) the hydroxyl group or acid group-containing resin and (D) the blocked isocyanate, which in turn causes (D) the blocked isocyanate to inhibit the dispersion of the coloring agent. When the colored film is formed in the non-display area of ​​the cover lens, a low diffuse reflectance is preferable from an aesthetic standpoint.

[0017] The hydroxyl value, according to JIS K0070 (1992), refers to the number of mg of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group when 1 g of hydroxyl group or acid group-containing resin is acetylated (unit: mgKOH / g). The acid value, according to JIS K0070 (1992), refers to the number of mg of potassium hydroxide required to neutralize 1 g of hydroxyl group or acid group-containing resin (unit: mgKOH / g).

[0018] (A) The weight-average molecular weight (Mw) of the hydroxyl group or acid group-containing resin 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 5,000 or more and 150,000 or less, and more preferably 10,000 or more and 150,000 or less. Here, the weight-average molecular weight (Mw) refers to the value obtained by analysis using gel permeation chromatography with tetrahydrofuran as the carrier and converted using a calibration curve with standard polystyrene.

[0019] (A) Examples of hydroxyl groups or acidic groups contained in a hydroxyl group or acidic group-containing resin include hydroxyl groups, carboxyl groups, carboxylic acid anhydrides, sulfonic acid groups, and phosphate groups. Two or more of these may be included. Among these, hydroxyl groups or carboxyl groups are particularly preferred from the viewpoint of adhesion after reliability testing of the coating film and low-temperature curing properties.

[0020] (A) The content of hydroxyl group or acid group-containing resin is preferably 10 to 99% by mass, and more preferably 25 to 85% by mass, based on 100% by mass of total solids, from the viewpoint of storage stability of the pigment dispersion, curability of the colored resin composition, and adhesion of the resulting colored film to the substrate. Here, solids refer to the components of the composition other than the solvent. The solids include (A) hydroxyl group or acid group-containing resin, (B) colorant, (C) dispersant, (D) blocked isocyanate, and other additives. The curability of the colored resin composition and the adhesion of the colored film to the substrate are also affected by the content of (D) blocked isocyanate, which will be described later.

[0021] (B) Examples of the coloring material include organic pigments, inorganic pigments, or dyes. Organic pigments or inorganic pigments are preferred in order to improve the heat resistance, reliability, and light resistance of the colored film.

[0022] Examples of the organic pigments include, for example, diketopyrrolopyrrole-based pigments; azo-based pigments such as azo, disazo, and polyazo; phthalocyanine-based pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine; anthraquinone-based pigments such as aminoanthraquinone, diaminoanthraquinone, anthrapyrimidine, flavanthrone, anthraanthrone, indanthrone, pyranthrone, and violanthrone; quinacridone-based pigments; dioxazine-based pigments; perinone-based pigments; perylene-based pigments; thioindigo-based pigments; isoindoline-based pigments; isoindolinone-based pigments; quinophthalone-based pigments; fluorene-based pigments; metal complex-based pigments, and the like.

[0023] Examples of the inorganic pigments include, for example, titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, red iron oxide, molybdenum red, molybdate orange, chrome vermilion, lead yellow, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chromium green, victoria green, ultramarine, dark blue, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, cobalt violet, and the like.

[0024] Examples of the dyes include, for example, azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methine dyes, polymethine dyes, and the like.

[0025] Examples of black colorants include black organic pigments, mixed organic pigments, and inorganic pigments. Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone pigments. Examples of mixed organic pigments include those obtained by mixing two or more pigments having colors such as red, blue, green, purple, yellow, magenta, and cyan to produce a pseudo-black color. Examples of black inorganic pigments include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; and oxides, composite oxides, sulfides, nitrides, and oxynitrides of the above metals.

[0026] Examples of white colorants include titanium dioxide, barium carbonate, zirconium oxide, calcium carbonate, barium sulfate, alumina white, and silicon dioxide.

[0027] These colorants may contain two or more types.

[0028] In the colored resin composition of the present invention, (B) the coloring agent is preferably finely dispersed and in a stable dispersion state. If the dispersion of the coloring agent is insufficient, the presence of coarse particles of the coloring agent in the resulting colored film will cause unevenness in the film density, which is thought to be a factor in the deterioration of the adhesion of the colored film after lightfastness tests and high temperature and high humidity tests. The average particle size of the coloring agent in the colored resin composition is preferably 30 to 200 nm, and more preferably 30 to 120 nm. As a means of achieving the above range for the average particle size of the coloring agent, it is preferable to use an acrylic dispersant having a basic group as a dispersant, and to stably and uniformly disperse the coloring agent in a fine state without re-aggregating it in the resin. More specifically, examples of methods for producing the colored resin composition include a method of micronizing the coloring agent by salt milling or a method of finely dispersing it by a bead mill described later.

[0029] The content of (B) colorant in the colored resin composition of the present invention is preferably 1 to 60% by mass based on 100% by mass of the total solid content. By setting the content of (B) colorant to 1 part by mass or more, the visible light shielding properties of the resulting colored film can be improved. Furthermore, since the colorant is a component that does not shrink during curing, a higher content of colorant reduces film stress and improves adhesion. From this viewpoint, a colorant content of 13% by mass or more is more preferable. On the other hand, if the content of (B) colorant is too high, the resin component responsible for the curing reaction decreases, which worsens the adhesion of the colored film. For this reason, a (B) colorant content of 60% by mass or less is preferred, and 48% by mass or less is more preferable.

[0030] In the colored resin composition of the present invention, (C) dispersant is an acrylic dispersant having a basic group. A dispersant is defined as having both a colorant affinity group that chemically bonds to or adsorbs to the surface of the colorant and a polymer chain or group that is solvent-friendly. An acrylic dispersant refers to a dispersant having a main chain formed by copolymerizing monomers containing (meth)acrylic groups. The main chain may be a block copolymer or a random copolymer, and may also have side chains such as a graft copolymer.

[0031] The dispersant, in the dispersion treatment described later, improves the wettability of the colorant to the dispersion medium, promotes the deaggregation of the colorant, stabilizes the particle size and viscosity of the colorant through steric hindrance and / or electrostatic repulsion effects, and further suppresses the occurrence of color separation during storage or application of the colored resin composition.

[0032] In the colored resin composition of the present invention, (C) the dispersant is selected to be an acrylic resin that is excellent in reliability such as light resistance and resistance to high temperature and high humidity. Furthermore, by having a basic group in the (C) dispersant, the dispersant is adsorbed onto the surface of the colorant, finely disperses the colorant during dispersion, stabilizes the dispersion state due to steric hindrance between the dispersants, and has the effect of suppressing thickening and re-aggregation over time. Examples of basic groups include primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, amide groups, imino groups, imidazoline groups, pyrrole groups, imidazole groups, benzimidazole groups, pyrazole groups, pyridine groups, pyrimidine groups, pyrazine groups, pyrrolidine groups, piperidine groups, piperazine groups, indole groups, indoline groups, purine groups, quinoline groups, isoquinoline groups, quinuclidine groups, and triazine groups. The dispersant may have one or more of these basic groups. Among these, dispersants containing at least one of a tertiary amino group and a quaternary ammonium base are preferred because they have good adsorption to the coloring material and high dispersibility, and dispersants containing both a tertiary amino group and a quaternary ammonium base are particularly preferred. When the adsorption to the coloring material is good, the amount of dispersant released into the colored film by detachment from the coloring material during the high temperature and high humidity test and the lightfastness test is reduced, which is thought to improve the adhesion of the colored film after the lightfastness test and the high temperature and high humidity test.

[0033] (C) If the amine value of the dispersant is too low, the adsorption to the coloring agent will be insufficient, and if the amine value is too high, the storage stability of the colored resin composition will decrease. For this reason, the amine value is preferably 1 mg KOH / g or more and 200 mg KOH / g or less, and more preferably 20 mg KOH / g or more and 150 mg KOH / g or less. The weight-average molecular weight (Mw) is preferably 500 or more and 150,000 or less, and more preferably 5,000 or more and 150,000 or less, from the viewpoint of the reliability of the colored film. In this invention, the amine value represents the number of mg of the acid and equivalent amount of KOH required to neutralize 1 g of the dispersant.

[0034] Examples of acrylic dispersants having a basic group include DISPERBYK®-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®-LPN6919, LPN21116, and LPN22102 (all manufactured by Bic Chemie). Among these, examples of acrylic dispersants containing at least one tertiary amino group and a quaternary ammonium base include DISPERBYK®-187, 190, 191, 194N, 199, 2000, 2001, 2006, 2009, 2010, 2012, 2013, 2015, 2022, 2025, 2050, 2055, DISPERBYK®-LPN6919, and LPN21116. An example of an acrylic dispersant having both a tertiary amine and a quaternary ammonium salt is DISPERBYK®-LPN21116.

[0035] (C) From the viewpoint of improving dispersion stability, the content of the dispersant is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of the (B) coloring agent. On the other hand, from the viewpoint of improving the adhesion and reliability of the colored film, the content of the dispersant is preferably 100 parts by mass or less, and more preferably 60 parts by mass or less, per 100 parts by mass of the coloring agent.

[0036] (D) Blocked isocyanates are compounds having two or more isocyanate groups blocked by a blocking agent. Because the blocking agent dissociates upon heating and the isocyanate groups are regenerated, blocked isocyanates have a long pot life, and inks containing them have excellent viscosity stability. In the colored resin composition of the present invention, blocked isocyanates are used as curing agents. Blocked isocyanates regenerate isocyanate groups by dissociating (deprotecting) the blocking agent upon heating at relatively low temperatures. The regenerated isocyanate groups react thermally with the hydroxyl groups or acid groups of the (A) hydroxyl group or acid group-containing resin, causing the ink to harden.

[0037] The types of isocyanates are not particularly limited, but include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, dimers or trimers obtained by modification of diisocyanates, and compounds containing terminal isocyanate groups. These may be used alone or in combination. Examples of aromatic diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, and dianisidine diisocyanate. Examples of aliphatic diisocyanates include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter HMDI), and 2,2,4-trimethyl-1,6-hexamethylene diisocyanate. Examples of alicyclic diisocyanates include lysine diisocyanate, isophorone diisocyanate (hereinafter IPDI), 1,3-bis(isocyanatomethyl)-cyclohexane, and 4,4'-dicyclohexylmethane diisocyanate. Furthermore, dimers or trimers obtained by modifying these diisocyanates are also included. Modification methods include biuretization and isocyanuration. Alternatively, examples include terminal isocyanate group-containing compounds obtained by reacting the aforementioned diisocyanate compounds or polyisocyanate compounds with active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, ethanolamine, polyester polyols, polyether polyols, and polyamides.

[0038] Examples of known blocking agents include phenol, methyl ethyl ketoxime, and sodium bisulfite. When selecting a resin such as polycarbonate or PET film as the substrate, it is preferable to use a blocked isocyanate in which the blocking agent dissociates at a lower temperature, releasing the isocyanate group.

[0039] Examples of blocking agents that can be dissociated at lower temperatures include active methylene compounds or pyrazole compounds. Examples of active methylene compounds include meldrumic acid, dialkyl malonate, alkyl acetoacetate, 2-acetoacetoxyethyl methacrylate, acetylacetone, and ethyl cyanoacetate. 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, and 3-methyl-5-phenylpyrazole. Diethyl malonate and 3,5-dimethylpyrazole are particularly preferred.

[0040] Blocked isocyanates are commercially available. For example, Coronate® AP Stable M, Coronate® 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all manufactured by Nippon Polyurethane Industries Co., Ltd.), Duranate® 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (all manufactured by Asahi Kasei Chemicals Corporation), Desmodule BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumijool® BL3175 (all manufactured by Sumika Bayer Urethane Co., Ltd.) can be preferably used.

[0041] The amounts of (A) hydroxyl group or acid group-containing resin and (D) blocked isocyanate are preferably selected so that each functional group is consumed after curing. For example, the amount of (D) blocked isocyanate is preferably 1 to 300 parts by mass, more preferably 5 to 150 parts by mass, and even more preferably 10 to 100 parts by mass, based on 100 parts by mass of (A) hydroxyl group or acid group-containing resin. When the amount of blocked isocyanate is within these ranges, the effect of efficiently curing the hydroxyl group or acid group-containing resin can be obtained.

[0042] The colored resin composition of the present invention preferably further contains (E) an organic solvent, as this improves its coatability. The (E) organic solvent has the effect of uniformly dissolving or dispersing (A) a hydroxyl group or acid group-containing resin, (B) a coloring agent, (C) a dispersant, and (D) a blocked isocyanate. As the (E) organic solvent, a compound with a boiling point of 110 to 250°C at atmospheric pressure is preferred. Since the colored resin composition of the present invention is expected to be applied by printing methods such as spin coaters, slit coaters, screen printing, inkjet printing, gravure printing, or bar coaters, if the boiling point is below 110°C, the drying rate of the organic solvent is fast, which can easily lead to problems with coating uniformity. On the other hand, if the boiling point exceeds 250°C, organic solvent may remain in the resulting colored film, which can worsen the chemical resistance of the colored film.

[0043] (E) Examples of organic solvents include ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, and alcohols.

[0044] 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 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, and the like. Examples of acetates include butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 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 monomethyl ether acetate, propylene glycol monoethyl ether acetate (hereinafter referred to as "PGMEA": boiling point 146.4°C), dipropylene glycol methyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate.Examples of esters include alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate. Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. Examples of aromatic hydrocarbons include toluene and xylene. Examples of amides include N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. Examples of alcohols include butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, and diacetone alcohol. Two or more of these may be included.

[0045] Among these, acetates are preferred in order to further stabilize the dispersion of the coloring agent. (E) The content of acetates in the organic solvent is preferably 50 to 100% by mass, and more preferably 70 to 100% by mass.

[0046] When forming a colored film by coating a substrate with a colored resin composition, the use of a die coating apparatus is becoming the mainstream method as substrate sizes increase. On the other hand, when forming a colored film as a decorative film for decorating cover lenses or for concealing near-infrared sensors and near-infrared cameras, it is necessary to form the colored film on small pieces of glass, and coating by a screen printing apparatus or inkjet apparatus is preferred. From the viewpoint of achieving suitable volatility and drying properties in these coating methods using die coating apparatuses, screen printing apparatuses, and inkjet apparatuses, it is preferable to contain two or more types of (E) organic solvents. From the viewpoint of making the film thickness of the coating obtained from the colored resin composition of the present invention uniform, improving the smoothness and tackiness of the surface, suppressing drying foreign matter in the nozzles of die coating apparatuses and inkjet apparatuses, and ensuring continuous printability of screen printing apparatuses, it is preferable to contain 3 to 90% by mass of an organic solvent with a boiling point of 150 to 250°C in the (E) organic solvent, and more preferably 10 to 75% by mass.

[0047] In the colored resin composition of the present invention, the content of (E) organic solvent is preferably 50% by mass or more, and more preferably 70% by mass or more, from the viewpoint of uniformity of the film thickness of the coating film in the coating process. On the other hand, the content of (E) organic solvent is preferably 95% by mass or less, and more preferably 90% by mass or less, from the viewpoint of suppressing pigment sedimentation.

[0048] The colored resin composition of the present invention may contain a leveling agent. By including a leveling agent, the coatability and surface smoothness of the colored film can be improved. Examples of leveling agents include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine; cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride; amphoteric surfactants such as lauryldimethylamine oxide and laurylcarboxymethylhydroxyethylimidazolium betaine; nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and sorbitan monostearate; silicone-based surfactants with polydimethylsiloxane as the main skeleton; and fluorine-based surfactants. Two or more of these may be included. Examples of commercially available surfactants include "BYK(registered trademark)"-302, 333, 3550, and 392 (all manufactured by BYK Chemie).

[0049] A preferred method for producing the colored resin composition of the present invention is to first prepare a colored material dispersion with a high concentration of colorant by dispersing a resin solution containing (A) a hydroxyl group or acid group-containing resin, (B) a colorant, (C) a dispersant, and (E) an organic solvent using a disperser, and then adding (A) a hydroxyl group or acid group-containing resin, (D) a blocked isocyanate, and other components such as a surfactant as needed, and stirring. The obtained colored resin composition may be filtered as needed.

[0050] Examples of dispersers used for dispersion processing include ball mills, bead mills, sand grinders, three-roll mills, and high-speed impact mills. Among these, bead mills are preferred for their dispersion efficiency and fine dispersion capabilities. Examples of bead mills include ball mills, basket mills, pin mills, and dyno mills. Examples of beads used in bead mills include titania beads, zirconia beads, and zircon beads.

[0051] In the method for producing the colored resin composition of the present invention, it is preferable to perform a multi-stage dispersion treatment using a bead mill. For example, it is preferable to perform dispersion treatment using a bead mill with beads having an average bead diameter larger than 0.1 mmφ, and then perform dispersion treatment using a bead mill with beads having an average bead diameter of 0.1 mmφ or less. By performing dispersion treatment using a bead mill with beads having an average bead diameter larger than 0.1 mmφ, colorants with large crystallite sizes can be efficiently crushed. Subsequently, by performing dispersion treatment using a bead mill with minute beads having an average bead diameter of 0.1 mmφ or less, the energy supplied to the colorant can be reduced, and the surface activity of the colorant can be suppressed while achieving fine dispersion. This suppresses the re-aggregation of the colorant in the colored resin composition and allows for more uniform and fine dispersion. In this case, it is preferable that the bead mill be equipped with a separator that uses a centrifugal separation method capable of separating the minute beads from the dispersion liquid. Here, the average bead diameter refers to the number average value of the equivalent circular diameter of the beads. Specifically, the beads can be magnified 45 times using a stereomicroscope, and for 100 randomly selected beads, the longest and shortest diameters are measured for each. The average of these two values ​​is then used as the equivalent circle diameter, and the bead diameter can be determined by calculating the numerical average of these values.

[0052] A colored film can be obtained by curing the colored resin composition of the present invention. Regarding the light-shielding properties of the colored film formed in the non-display area of ​​the display, an OD value of 4.0 or higher is preferred, and an OD value of 4.5 or higher is more preferred, from the viewpoint of preventing light leakage from the backlight.

[0053] Next, a method for forming a decorative substrate by curing the colored resin composition of the present invention will be described. By applying the colored resin composition onto a substrate and curing it to form a colored film, a decorative substrate comprising a substrate and a colored film is obtained.

[0054] 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; film substrates such as PET film and COP film; and silicon wafers, ceramics, and gallium arsenide substrates. Examples of coating methods include rotary coating using a spinner, spray coating, die coating, roll coating, inkjet printing, screen printing, and gravure printing. The film thickness of the coated film can be appropriately selected depending on the coating method. Generally, the film thickness after drying is 1 to 150 μm.

[0055] The obtained coating film is dried to obtain a dried film. Examples of drying methods include heating, air drying, reduced pressure drying, and infrared irradiation. Examples of heating and drying equipment include ovens and hot plates. The drying temperature is preferably 50 to 150°C, and the drying time is preferably 1 minute to several hours. This drying process is expected to flatten the coating film by leveling and suppress the adhesion of foreign matter, but this drying process is not always necessary, and a colored film can be obtained by the heat treatment described later alone.

[0056] The obtained coating film can be cured by heat treatment (post-bake) to obtain a colored film. The heat treatment may be performed in air, under a nitrogen atmosphere, or under a vacuum. The heating temperature is preferably 70 to 300°C, and particularly preferably 80 to 180°C. If the substrate is a resin, the heating temperature can be selected according to the heat resistance temperature of the substrate; for example, if the substrate is polycarbonate, 80 to 120°C is preferred. The heating time is preferably 0.25 to 5 hours. During the heat treatment, the heating temperature may be changed continuously or in steps.

[0057] A decorative substrate comprising a substrate and a colored film made from a cured product of the colored resin composition of the present invention can be suitably used as a decorative substrate in display terminals such as smartphones, tablet PCs, and in-vehicle displays; a decorative substrate for concealing near-infrared sensors and near-infrared cameras for driver monitoring and gesture sensors in in-vehicle displays and in-vehicle instruments; and a decorative film for concealing LiDAR sensors. Furthermore, the colored film made from a cured product of the colored resin composition of the present invention can be suitably used as a light-shielding film such as a black matrix in a color filter of a liquid crystal display device, or as a colored partition inside an organic EL display. [Examples]

[0058] The present invention will be described in detail below with reference to examples and comparative examples, but the embodiments of the present invention are not limited thereto. Examples 8 and 16-18 are currently considered reference examples, while Examples 1-7 and 9-15 are embodiments of the present invention.

[0059] <Evaluation Method> [Adhesion] The adhesion of the colored films obtained in each example and comparative example was evaluated in accordance with JIS "K5600-5-6 (established on April 20, 1999)". Specifically, using a utility knife, 11 parallel lines were drawn vertically and horizontally at 1 mm intervals, so as to reach the substrate, creating 100 1 mm x 1 mm grids. Cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) was attached to the surface of the cut colored film, and rubbed with an eraser (JIS S6050 compliant product) to ensure adhesion between the tape and the colored film. Then, holding one end of the tape and keeping it perpendicular to the board, the tape was instantly peeled off the colored film. At this time, the proportion of the colored film that was peeled off was evaluated by visually checking the number of colored film squares that remained attached to the substrate out of the 100 colored film squares. The adhesion of the colored film was determined as follows based on the peeled area of ​​the squares, with a score of 4 or higher being considered acceptable. 5: Peeling area = 0% 4: Peeling area = <5% 3: Peeling area = 5-14% 2: Peeling area = 15-34% 1: Peeling area = 35%~64% 0: Peeling area = 65%~100%.

[0060] [Viscosity measurement] The viscosity of the colored resin compositions was measured at 25°C using an E-type viscometer (VISCOMETER TV-25, manufactured by Toki Sangyo Co., Ltd.) immediately after preparation and after 30°C / 1 week. Based on the ratio (b) / (a), where (a) is the viscosity immediately after preparation and (b) is the viscosity after 30°C / 1 week, the viscosity stability of the colored resin compositions at room temperature was determined as follows, with A and B being considered acceptable. 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).

[0061] [High temperature and high humidity resistance] The colored films obtained in each example and comparative example were treated with a PC-242HS-E manufactured by Hirayama Seisakusho at 121°C, 2 atm, and 100% humidity for 24 hours, and then evaluated for adhesion.

[0062] [Lightfastness] The colored films obtained in each example and comparative example were tested using a Q-Lab Q-SUN xenon tester Xe-3, with a Xe lamp X-1800 as the light source, at a wavelength of 420 nm, with an illuminance of 1.2 W / m². 2 After irradiating with ultraviolet light at the specified intensity for 300 hours, the [adhesion] was evaluated.

[0063] [Average particle size of colorants] A dynamic light scattering particle size analyzer (UPA-EX150, manufactured by Microtrac-Bell) was set to a temperature of 20±1℃, and the measured value (D50) obtained by measuring a colorant dispersion or colored resin composition diluted 400 times with propylene glycol monomethyl ether acetate was taken as the average particle size of the colorant particles.

[0064] [Diffuse reflection] For the colored films obtained in each example and comparative example, the diffuse reflectance chromaticity (SCE) was measured for light incident from the transparent substrate side using a spectrophotometer (CM-2600d; Konica Minolta, Inc.) calibrated with a white calibration plate (CM-A145; Konica Minolta, Inc.), under measurement conditions of standard light source D65 (color temperature 6504K), viewing angle 2° (CIE1976), atmospheric pressure, and 20°C. (L) was used as an index of the diffuse reflectance of the colored film. * ) was evaluated. The colored film formed in the non-display area of ​​the cover lens was evaluated from the perspective of design. * A low value is preferable.

[0065] [Solvent resistance] The film thickness of the colored films obtained in each example and comparative example was measured using a contact film thickness gauge, Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.). A white cotton cloth (Kanakin No. 3) thoroughly impregnated with isopropyl alcohol, the test solvent, was placed over the colored film as a friction element and measured under constant load conditions (300 g / cm²) using a JSPS-type rubbing tester. 2 After performing a rubbing test (10 back-and-forth passes) using the rubbing test, the film thickness was measured again. The solvent resistance of the colored film was determined from the change in film thickness before and after the rubbing test using the following formula. A value close to 100% was considered good, and a value of 80% or higher was considered acceptable. Solvent resistance (%) = Film thickness after rubbing test (μm) × 100 / Film thickness before rubbing test (μm) Solvent resistance is evaluated to quantitatively assess the degree of hardening during low-temperature firing.

[0066] (Synthesis Example 1: Synthesis of a hydroxyl group or acid group-containing resin (P-1)) 100 g of isopropyl alcohol was placed in a 1000 cc four-necked flask and kept at 80°C in an oil bath. The flask was nitrogen-sealed and stirred while 30 g of methyl methacrylate, 40 g of styrene, and 30 g of methacrylic acid were added dropwise over 30 minutes using a dropper funnel. A mixture of these monomers, along with 2 g of N,N-azobisisobutyronitrile as an initiator, was added dropwise. The reaction continued for 4 hours, after which 1 g of hydroquinone monomethyl ether was added, and the mixture was returned to room temperature to complete polymerization. Next, 100 g of isopropyl alcohol was added to this polymer solution, and while keeping the temperature at 75°C, 40 g of glycidyl methacrylate and 3 g of triethylbenzylammonium chloride were added and the mixture was reacted for 3 hours. After the reaction was complete, the resulting resin solution was reprecipitated with purified water, filtered, and dried to obtain a hydroxyl or acid group-containing resin (P-1) with a weight-average molecular weight of 15,000, a hydroxyl value of 0 mgKOH / g, and an acid value of 110 mgKOH / g. The hydroxyl value of the resin was determined according to JIS K0070 (1992), by measuring the amount of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl groups when 1 g of resin was acetylated. The weight-average molecular weight was measured using gel permeation chromatography (GPC) "HLC-8220GPC" (test equipment manufactured by Tosoh Corporation), with tetrahydrofuran as the carrier, and converted to polystyrene equivalent.

[0067] (Synthesis Example 2: Synthesis of hydroxyl group or acid group-containing resin (P-2)) 100 g of isopropyl alcohol was placed in a 1000 cc four-necked flask, maintained at 80°C in an oil bath, nitrogen-sealed, and while stirring, a mixture of 25 g of methyl methacrylate, 52 g of styrene, and 33 g of 2-hydroxyethyl methacrylate as monomers, and 2 g of N,N-azobisisobutyronitrile as an initiator was added dropwise over 30 minutes using a dropping funnel. After continuing the reaction for 4 hours, 1 g of hydroquinone monomethyl ether was added, and the mixture was returned to room temperature to complete polymerization. After the reaction was complete, the resulting resin solution was reprecipitated with purified water, filtered, and dried to obtain a hydroxyl or acid group-containing resin (P-2) with a weight-average molecular weight of 13,000, a hydroxyl value of 100 mg KOH / g, and an acid value of 0 mg KOH / g.

[0068] (Synthesis Example 3: Synthesis of hydroxyl group or acid group-containing resin (P-3)) Except for using 10 g of methyl methacrylate, 13 g of methacrylic acid, 21 g of styrene, and 72 g of 2-hydroxyethyl methacrylate as monomers, the same procedure as in Synthesis Example 2 was used to obtain a hydroxyl group or acid group-containing resin (P-3) with a weight-average molecular weight of 12,500, a hydroxyl value of 230 mg KOH / g, and an acid value of 60 mg KOH / g.

[0069] (Synthesis Example 4: Synthesis of hydroxyl group 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, the same procedure as in Synthesis Example 2 was used to obtain a hydroxyl group or acid group-containing resin (P-4) with a weight-average molecular weight of 14,000, a hydroxyl value of 0 mg KOH / g, and an acid value of 70 mg KOH / g.

[0070] (Synthesis Example 5: Synthesis of hydroxyl group 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, the same procedure as in Synthesis Example 2 was used to obtain a hydroxyl group or acid group-containing resin (P-5) with a weight-average molecular weight of 15,000, a hydroxyl value of 70 mg KOH / g, and an acid value of 0 mg KOH / g.

[0071] (Synthesis Example 6: Synthesis of hydroxyl group or acid group-containing resin (P-6)) Except for using 47 g of methyl methacrylate, 5 g of methacrylic acid, 42 g of styrene, and 10 g of 2-hydroxyethyl methacrylate as monomers, the same procedure as in Synthesis Example 2 was used to obtain a hydroxyl group or acid group-containing resin (P-6) with a weight-average molecular weight of 145,000, a hydroxyl value of 30 mg KOH / g, and an acid value of 40 mg KOH / g. Table 1 shows the hydroxyl value and acid value of synthesis examples 1 to 6.

[0072] [Table 1]

[0073] (Manufacturing Example 1: Manufacturing of Red Pigment PR177-1) 200g of BASF's "Cromophtal® Red A3B," 2400g of sodium chloride, and 400g of diethylene glycol were placed in a kneader (Moriyama Seisakusho Co., Ltd., S-type kneader (product name)) and kneaded at 70°C for 8 hours. Next, this mixture was added to approximately 10L of warm water and stirred in a high-speed mixer for 1 hour while heating to 40°C to form a slurry. After that, it was filtered, washed with water to remove the sodium chloride and diethylene glycol, and vacuum-dried at 80°C for 24 hours to obtain the red pigment PR177-1.

[0074] (Manufacturing Example 2: Manufacturing of blue pigment PB15:6-1) 200g of "LIONOL® BLUE ES" manufactured by Toyo Color Co., Ltd., 2400g of sodium chloride, and 400g of diethylene glycol were placed in a kneader (S-type kneader (product name) manufactured by Moriyama Seisakusho Co., Ltd.) and kneaded at 70°C for 8 hours. Next, this mixture was added to approximately 10L of warm water and stirred with a high-speed mixer for 1 hour while heating to 40°C to form a slurry. After that, it was filtered and washed with water to remove the sodium chloride and diethylene glycol, and vacuum dried at 80°C for 24 hours to obtain the blue pigment PB15:6-1.

[0075] (Manufacturing Example 3: Manufacturing of yellow pigment PY150-1) 200g of Lanxess "E-4GN", 2400g of sodium chloride, and 400g of diethylene glycol were placed in a kneader (Moriyama Seisakusho Co., Ltd., S-type kneader (product name)) and kneaded at 70°C for 8 hours. Next, this mixture was added to approximately 10L of warm water and stirred with a high-speed mixer for 1 hour while heating to 40°C to form a slurry. After that, it was filtered and washed with water to remove the sodium chloride and diethylene glycol, and vacuum dried at 80°C for 24 hours to obtain the yellow pigment PY150-1.

[0076] (Manufacturing Example 4: Manufacturing of Bisbenzofuran Pigment Bk-1) As a bisbenzofuran pigment, 200g of BASF's "Irgaphor®" Black S0100CF, 2400g of sodium chloride, and 400g of diethylene glycol were placed in a kneader (Moriyama Seisakusho Co., Ltd., S-type kneader (product name)) and kneaded at 70°C for 8 hours. Next, this mixture was added to approximately 10L of warm water and stirred with a high-speed mixer for 1 hour while heating to 40°C to form a slurry. After filtering and washing with water to remove sodium chloride and diethylene glycol, it was vacuum-dried at 80°C for 24 hours to obtain the bisbenzofuran pigment Bk-1.

[0077] (Manufacturing Example 5: Manufacturing of Colorant Dispersion (DP-1)) 175 g of high-resistance carbon black TPK1227R (manufactured by Cabot Co., Ltd.), 179 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, 63 g of "DISPERBYK®" LP N6919 (manufactured by Bic Chemie, 20% by mass solution of propylene glycol monomethyl ether acetate) as an acrylic dispersant having a tertiary amino group as a basic group, and 584 g of PGMEA were placed in a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion. The obtained preliminary dispersion was supplied to a Kotobuki Kogyo Co., Ltd. Ultra Apex Mill UAM015 disperser equipped with a centrifugal separator packed with 75% by volume of zirconia beads with a bead diameter of 0.30 mmφ, and dispersion was carried out at a rotation speed of 9 m / s for 20 minutes. Next, the liquid after dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads with a diameter of 0.05 mmφ, and dispersion was carried out at a rotation speed of 11 m / s for 90 minutes to obtain a colorant dispersion DP-1 with a solid content concentration of 25% by mass and a colorant / (resin + dispersant) (mass ratio) of 70 / 30.

[0078] (Manufacturing Example 6: Manufacturing of Colorant Dispersion (DP-2)) 175 g of high-resistance carbon black TPK1227R (manufactured by Cabot Co., Ltd.), 179 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, 31 g of "DISPERBYK®" LP N21116 (manufactured by Bic Chemie, 40% by mass solution of propylene glycol monomethyl ether acetate) as an acrylic dispersant having a tertiary amino group and a quaternary ammonium base as basic groups, and 615 g of PGMEA were placed in a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion. The obtained preliminary dispersion was supplied to a Kotobuki Kogyo Co., Ltd. Ultra Apex Mill UAM015 disperser equipped with a centrifugal separator packed with 75% by volume of zirconia beads with a bead diameter of 0.30 mmφ, and dispersed at a rotation speed of 9 m / s for 20 minutes. Next, the liquid after dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads with a bead diameter of 0.05 mmφ, and dispersion was carried out at a rotation speed of 11 m / s for 90 minutes to obtain a colorant dispersion liquid DP-2 with a solid content concentration of 25% by mass and a colorant / (resin + dispersant) (mass ratio) of 70 / 30.

[0079] (Manufacturing Example 7: Manufacturing of Colorant Dispersion (DP-3)) 120 g of the aforementioned 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, 50 g of "DISPERBYK®" LP N21116 (manufactured by Bic Chemie, 40% by mass solution of propylene glycol monomethyl ether acetate) as an acrylic dispersant having a tertiary amino group and a quaternary ammonium base as basic groups, and 659 g of PGMEA were placed in a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion. The obtained preliminary dispersion was supplied to a Kotobuki Kogyo Co., Ltd. Ultra Apex Mill UAM015 disperser equipped with a centrifugal separator packed with 75% by volume of zirconia beads with a bead diameter of 0.50 mmφ, and dispersed at a rotation speed of 12 m / s for 20 minutes. Next, the liquid after dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads with a diameter of 0.05 mmφ, and dispersion was carried out at a rotation speed of 8 m / s for 90 minutes to obtain a colorant dispersion DP-3 with a solid content concentration of 20% by mass and a colorant / (resin + dispersant) (mass ratio) of 60 / 40.

[0080] (Manufacturing Example 8: Manufacturing of Colorant Dispersion (DP-4)) A colorant dispersion DP-4 was obtained in the same manner as in Production Example 7, except that the blue pigment PB15:6-1 was used instead of the red pigment PR177-1, with a solid content concentration of 20% by mass and a colorant / (resin + dispersant) (mass ratio) = 60 / 40.

[0081] (Manufacturing Example 9: Manufacturing of Colorant Dispersion (DP-5)) A colorant dispersion DP-5 was obtained in the same manner as in Production Example 7, except that the yellow pigment PY150-1 was used instead of the red pigment PR177-1, with a solid content concentration of 20% by mass and a colorant / (resin + dispersant) (mass ratio) = 60 / 40.

[0082] (Manufacturing Example 10: Manufacturing of a colorant dispersion (DP-6)) A colorant dispersion DP-6 was obtained in the same manner as in Production Example 7, except that the bisbenzofuranone pigment Bk-1 was used instead of the red pigment PR177-1, with a solid content concentration of 20% by mass and a colorant / (resin + dispersant) (mass ratio) = 60 / 40.

[0083] (Manufacturing Example 11: Manufacturing of Colorant Dispersion (DP-7)) 175g of high-resistance carbon black TPK1227R (manufactured by Cabot Co., Ltd.), 179g of a 35% by mass solution of propylene glycol monomethyl ether acetate (PGMEA) of the acrylic resin (P-1) obtained in Synthesis Example 1, 31g of "DISPERBYK®" LP N21116 (manufactured by Bic Chemie, 40% by mass solution of propylene glycol monomethyl ether acetate) as an acrylic dispersant having a tertiary amino group and a quaternary ammonium base as basic groups, and 615g of PGMEA were placed in a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion. The obtained preliminary 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 to obtain a colorant dispersion DP-7 with a solid content concentration of 20% by mass and a colorant / (resin + polymer dispersant) (mass ratio) of 60 / 40.

[0084] (Manufacturing Example 12: Manufacturing of Colorant Dispersion (DP-8)) 175g of high-resistance carbon black TPK1227R (manufactured by Cabot Co., Ltd.), 179g of a 35% by mass solution of propylene glycol monomethyl ether acetate (PGMEA) of the acrylic resin (P-1) obtained in Synthesis Example 1, 24g of "DISPERBYK®" 167 (manufactured by Bic Chemie, 52% by mass solution of butyl acetate) as a urethane dispersant, and 622g of PGMEA were placed in a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion. The obtained preliminary dispersion was supplied to a Kotobuki Kogyo Co., Ltd. Ultra Apex Mill UAM015 disperser equipped with a centrifugal separator packed with 0.30 mmφ zirconia beads at 75% by volume, and dispersed at a rotation speed of 9 m / s for 20 minutes. Next, the liquid after dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads with a bead diameter of 0.05 mmφ, and dispersion was carried out at a rotation speed of 11 m / s for 90 minutes to obtain a colorant dispersion liquid DP-8 with a solid content concentration of 25% by mass and a colorant / (resin + dispersant) (mass ratio) of 70 / 30. Table 2 shows the composition and dispersion conditions for manufacturing examples 5 to 12.

[0085] [Table 2]

[0086] (Example 1) To 31.43 g of a colorant dispersion (DP-1), 26.56 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-1) in PGMEA, 6.43 g of a blocking agent consisting of Coronate® BI-301 (manufactured by Tosoh Corporation) or Solvesso® 100 (manufactured by Exxon Chemicals, Inc.) 75% by mass solution, which is an oxime-based blocking agent or blocking isocyanate, and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by BY Chemie Inc.) in PGMEA were added to 36.98 g of PGMEA to obtain a colored resin composition PC-1 with a total solids concentration of 22% by mass and a colorant content of 25 parts by mass per 100 parts by mass of total solids.

[0087] The obtained colored resin composition PC-1 was applied to an easily adhesive layer of polyester film (Toray Industries, Inc., Lumirror® U48, film thickness: 100 μm) using a spinner (1H-DS) manufactured by Mikasa Corporation to form a coated film. The coated film was heated and dried in an oven at 90°C for 30 minutes to obtain colored film C-1. The results of evaluating this colored film C-1 using the method described above are shown in Table 4.

[0088] (Example 2) A colored resin composition PC-2 was obtained in the same manner as in Example 1, except that a colored agent dispersion (DP-2) was used instead of a colored agent dispersion (DP-1). The obtained colored resin composition PC-2 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0089] (Example 3) To 31.43 g of a colorant dispersion (DP-2), 26.56 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-1) in PGMEA, 6.89 g of Duranate® SBB-70P (manufactured by Asahi Kasei Corporation, 70% by mass solution of PGMEA) as a blocking isocyanate, which is a pyrazole-based blocking agent, and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by BYChemie) in PGMEA were added to 34.91 g of PGMEA to obtain a colored resin composition PC-3 with a total solids concentration of 22% by mass and a colorant content of 25 parts by mass per 100 parts by mass of total solids. The obtained colored resin composition PC-3 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0090] (Example 4) To 31.43 g of a colorant dispersion (DP-2), 26.56 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-1) PGMEA, 8.04 g of Duranate® MF-K60B (manufactured by Asahi Kasei Corporation, 60% by mass solution of n-butyl acetate / n-butanol), an active methylene-based blocking agent, and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by Bic Chemie Co., Ltd.) PGMEA were added to 33.77 g of PGMEA to obtain a colored resin composition PC-4 with a total solids concentration of 22% by mass and a colorant content of 25 parts by mass per 100 parts by mass of total solids. The obtained colored resin composition PC-4 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0091] (Example 5) A colored resin composition PC-5 was obtained in the same manner as in Example 3, except that a hydroxyl group or acid group-containing resin (P-2) was used instead of a hydroxyl group or acid group-containing resin (P-1). The obtained colored resin composition PC-5 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0092] (Example 6) To 22.92 g of a colorant dispersion (DP-3), 16.04 g of a colorant dispersion (DP-4), and 6.88 g of a colorant dispersion (DP-5), 23.27 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-1) in PGMEA, 6.67 g of Duranate® SBB-70P (manufactured by Asahi Kasei Corporation) as a blocking isocyanate, which is a pyrazole-based blocking agent, and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by BYChemie Inc.) in PGMEA were added to 24.03 g of PGMEA to obtain a colored resin composition PC-6 with a total solids concentration of 22% by mass and a colorant content of 25 parts by mass per 100 parts by mass of total solids. The obtained colored resin composition PC-6 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0093] (Example 7) To 45.83 g of a colorant dispersion (DP-6), 23.27 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-1) in PGMEA, 6.67 g of Duranate® SBB-70P (manufactured by Asahi Kasei Corporation) as a blocking isocyanate, which is a pyrazole-based blocking agent, and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by BYK Chemie) in PGMEA were added to a solution dissolved in 24.03 g of PGMEA to obtain a colored resin composition PC-7 with a total solids concentration of 22% by mass and a colorant content of 25 parts by mass per 100 parts by mass of total solids. The obtained colored resin composition PC-7 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0094] (Example 8) A colored resin composition PC-8 was obtained in the same manner as in Example 3, except that a colored agent dispersion (DP-7) was used instead of a colored agent dispersion (DP-2). The obtained colored resin composition PC-8 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0095] (Example 9) To 18.86 g of a colorant dispersion (DP-2), 33.52 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-1) in PGMEA, 7.90 g of Duranate® SBB-70P (manufactured by Asahi Kasei Corporation) as a pyrazole-based blocking agent (blocking isocyanate), and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by BY Chemie) in PGMEA were added to a solution dissolved in 39.52 g of PGMEA to obtain a colored resin composition PC-9 with a total solids concentration of 22% by mass and a colorant content of 15 parts by mass per 100 parts by mass of total solids. The obtained colored resin composition PC-9 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0096] (Example 10) To 56.57 g of a colorant dispersion (DP-2), 12.64 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-1) in PGMEA, 4.87 g of a block isocyanate (Duranate®) SBB-70P (manufactured by Asahi Kasei Corporation) as a pyrazole-based blocking agent, and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by BYChemie) in PGMEA were added to 25.71 g of PGMEA to obtain a colored resin composition PC-10 with a total solids concentration of 22% by mass and a colorant content of 45 parts by mass per 100 parts by mass of total solids. The obtained colored resin composition PC-10 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0097] (Example 11) To 12.57 g of a colorant dispersion (DP-2), 37.00 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-1) in PGMEA, 8.41 g of Duranate® SBB-70P (manufactured by Asahi Kasei Corporation) as a blocking isocyanate, which is a pyrazole-based blocking agent, and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by BYChemie Inc.) in PGMEA were added to 41.82 g of PGMEA to obtain a colored resin composition PC-11 with a total solids concentration of 22% by mass and a colorant content of 10 parts by mass per 100 parts by mass of total solids. The obtained colored resin composition PC-11 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0098] (Example 12) To 62.86 g of a colorant dispersion (DP-2), 9.16 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-1) in PGMEA, 4.37 g of Duranate® SBB-70P (manufactured by Asahi Kasei Corporation) as a blocking isocyanate, which is a pyrazole-based blocking agent, and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by BYChemie Inc.) in PGMEA were added to 23.41 g of PGMEA to obtain a colored resin composition PC-12 with a total solids concentration of 22% by mass and a colorant content of 50 parts by mass per 100 parts by mass of total solids. The obtained colored resin composition PC-12 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0099] (Example 13) To 31.43 g of a colorant dispersion (DP-2), 17.37 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-1) in PGMEA, 11.49 g of a block isocyanate (Duranate®) SBB-70P (manufactured by Asahi Kasei Corporation) as a pyrazole-based blocking agent, and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by BYChemie) in PGMEA were added to 39.51 g of PGMEA to obtain a colored resin composition PC-13 with a total solids concentration of 22% by mass and a colorant content of 25 parts by mass per 100 parts by mass of total solids. The obtained colored resin composition PC-13 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0100] (Example 14) To 31.43 g of a colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-1) in PGMEA, 2.30 g of a block isocyanate (Duranate®) SBB-70P (manufactured by Asahi Kasei Corporation) as a pyrazole-based blocking agent, and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by BYChemie) in PGMEA were added to 30.32 g of PGMEA to obtain a colored resin composition PC-14 with a total solids concentration of 22% by mass and a colorant content of 25 parts by mass per 100 parts by mass of total solids. The obtained colored resin composition PC-14 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0101] (Example 15) To 31.43 g of a colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-3) in PGMEA, 2.30 g of Duranate® SBB-70P (manufactured by Asahi Kasei Corporation) as a blocking isocyanate, which is a pyrazole-based blocking agent, and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by BY Chemie Inc.) in PGMEA were added to 30.32 g of PGMEA to obtain a colored resin composition PC-15 with a total solids concentration of 22% by mass and a colorant content of 25 parts by mass per 100 parts by mass of total solids. The obtained colored resin composition PC-15 was evaluated in the same manner as in Example 1. The results are shown in Table 4. (Example 16) To 31.43 g of a colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-4) in PGMEA, 2.30 g of a block isocyanate (Duranate®) SBB-70P (manufactured by Asahi Kasei Corporation) as a pyrazole-based blocking agent, and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by BY Chemie) in PGMEA were added to 30.32 g of PGMEA to obtain a colored resin composition PC-16 with a total solids concentration of 22% by mass and a colorant content of 25 parts by mass per 100 parts by mass of total solids. The obtained colored resin composition PC-16 was evaluated in the same manner as in Example 1. The results are shown in Table 4. (Example 17) To 31.43 g of a colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-5) in PGMEA, 2.30 g of a block isocyanate (Duranate®) SBB-70P (manufactured by Asahi Kasei Corporation) as a pyrazole-based blocking agent, and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by BY Chemie) in PGMEA were added to 30.32 g of PGMEA to obtain a colored resin composition PC-17 with a total solids concentration of 22% by mass and a colorant content of 25 parts by mass per 100 parts by mass of total solids. The obtained colored resin composition PC-17 was evaluated in the same manner as in Example 1. The results are shown in Table 4. (Example 18) To 31.43 g of a colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-6) in PGMEA, 2.30 g of a block isocyanate (Duranate®) SBB-70P (manufactured by Asahi Kasei Corporation) as a pyrazole-based blocking agent, and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by BY Chemie) in PGMEA were added to 30.32 g of PGMEA to obtain a colored resin composition PC-18 with a total solids concentration of 22% by mass and a colorant content of 25 parts by mass per 100 parts by mass of total solids. The obtained colored resin composition PC-18 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0102] (Comparative Example 1) A colored resin composition PC-19 was obtained in the same manner as in Example 3, except that a colored agent dispersion (DP-8) was used instead of a colored agent dispersion (DP-2). The obtained colored resin composition PC-19 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0103] (Comparative Example 2) To 31.43 g of a colorant dispersion (DP-2), 26.56 g of a 35% by mass solution of hydroxyl group or acid group-containing resin (P-1) PGMEA, 4.83 g of the epoxy resin "Tecmore" VG-3101L (manufactured by Printec Co., Ltd.) instead of blocked isocyanate, and 0.20 g of a 10% by mass solution of the silicone-based surfactant "BYK®" 333 (manufactured by BY Chemie Co., Ltd.) PGMEA were added to 36.98 g of PGMEA to obtain a colored resin composition PC-20 with a total solids concentration of 22% by mass and a colorant content of 25 parts by mass per 100 parts by mass of total solids. The obtained colored resin composition PC-20 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0104] [Table 3]

[0105] [Table 4]

[0106] The colored resin composition of the example exhibits excellent viscosity stability and curability during low-temperature firing, and high adhesion after lightfastness and high-temperature / high-humidity tests. On the other hand, the colored resin composition of Comparative Example 1 exhibits insufficient viscosity stability, low adhesion, and poor adhesion after lightfastness and high-temperature / high-humidity tests. It also exhibits insufficient curability during low-temperature firing. Furthermore, the colored resin composition of Comparative Example 2 exhibits insufficient viscosity stability and curability during low-temperature firing. [Industrial applicability]

[0107] The colored resin composition of the present invention can be suitably used as a black decorative ink for forming a light-shielding film in the non-display area of ​​a cover lens for an in-vehicle display or the like.

Claims

1. A colored resin composition comprising (A) a hydroxyl group or acid group-containing resin, (B) a coloring agent, (C) a dispersant, and (D) a blocked isocyanate, wherein (C) the dispersant is an acrylic dispersant having a basic group, (A) the hydroxyl group or acid group-containing resin having a total acid value and hydroxyl group value of 100 to 300 mg KOH / g, (B) the coloring agent having an average particle size of 30 to 120 nm in the colored resin composition, and (D) the blocked isocyanate comprising at least one blocking agent selected from active methylene compounds and pyrazole compounds.

2. The colored resin composition according to claim 1, wherein the (C) dispersant contains at least one of a tertiary amino group and a quaternary ammonium base.

3. The colored resin composition according to claim 1 or 2, wherein the content of the (D) blocked isocyanate is 5 parts by mass or more and 150 parts by mass or less per 100 parts by mass of the content of the (A) hydroxyl group or acid group-containing resin.

4. The colored resin composition according to any one of claims 1 to 3, wherein the content of the coloring agent (B) is 13 to 48% by mass of 100% by mass of the total solids.

5. The colored resin composition according to any one of claims 1 to 4, further comprising (E) an organic solvent.

6. A colored film comprising a cured product of a colored resin composition according to any one of claims 1 to 5.

7. A decorative substrate comprising a substrate and the colored film described in claim 6.

Images