TWI703192B - Colored resin composition - Google Patents

Abstract

The object of the present invention is to provide a colored resin composition that suppresses repulsion or unevenness and can form a colored coating film with good appearance even when it is applied by spraying or inkjet. The present invention is a coloring resin composition, which is a coloring resin composition containing at least (A) a coloring material, (B) a binder resin, (C) an organic solvent, and two or more types of (D) surfactants, which contains (D1) Polyether modified silicone surfactants and (D2) silicon modified acrylic surfactants are used as the aforementioned surfactants, and the total content of the aforementioned surfactants (D1) and (D2) is composed of colored resin The content is more than 200ppm and less than 1500ppm.

Description

Colored resin composition

The present invention relates to a colored resin composition containing at least a colored material, a binder resin, an organic solvent, and two or more surfactants; and a colored film and a decorative substrate for a touch panel using the colored resin composition.

Traditionally, touch panel devices are generally mounted on the front of display panels such as liquid crystal display devices, and in general, a cover glass formed by printing a black ink composition to form a light-shielding film is bonded to the front of the touch panel . However, in the configuration of such an external touch panel, there are problems of increased thickness and weight.

Therefore, in recent years, for display devices with touch sensor functions, a cover glass integrated touch panel has been proposed, which is to form a conductive film directly on the cover glass and a piece of glass for the sensor to function as a cover The function of both glass and touch sensor. This type of cover glass integrated touch panel is formed with a light shielding layer on the glass, and is further formed with a conductive film, ITO and other wiring on the light shielding layer. Regarding the manufacturing method of the cover glass integrated touch panel, for example, a method has been proposed, which includes the steps of forming a light shielding material on a glass substrate by a screen printing method and grinding; The step of overcoat layer; the step of forming a touch panel sensor on the overcoat layer; and the step of cutting the glass substrate together with the touch panel sensor as a whole (for example, refer to Patent Document 1). In addition, with regard to the black composition suitable for the decoration of such touch panels, a black composition has been proposed, which contains at least two types of organic pigments, binder resins, silane coupling agents, and photopolymerizable monomers (for example, Refer to Patent Document 2).

However, in such a manufacturing method, there is a problem of insufficient glass strength. Therefore, the use of glass cut into individual pieces and chemically strengthened to form a cover glass integrated touch panel has been reviewed. In addition, for the purpose of improving the design, a review has been conducted to form a cover glass integrated touch panel using curved glass.

The traditional method of applying light-shielding material by a slit coater or spinner to individual pieces of glass or curved glass is difficult from the viewpoint of productivity, as an alternative method Examples include coating by inkjet or spraying.

唑啉基的樹脂、烷二醇、界面活性劑、及水(例如，參照專利文獻3)；或一種噴墨用印墨，其含有：含有羥基的羧酸酯、界面活性劑、及水(例如，參照專利文獻4)。 On the other hand, various reviews regarding resin compositions suitable for inkjet coating have been conducted. For example, a coating liquid for inkjet has been proposed, which contains:

An oxazoline-based resin, alkanediol, a surfactant, and water (for example, refer to Patent Document 3); or an inkjet ink containing: a hydroxyl-containing carboxylic acid ester, a surfactant, and water (for example, , Refer to Patent Document 4).

Prior art literature Patent literature

Patent Document 1 JP 2012-155644 A

Patent Document 2 JP 2015-200775 A

Patent Document 3 US Patent Application Publication No. 2013/29045 Specification

Patent Document 4 JP 2013-87207 A

[Summary of the invention]

However, the coating liquids or printing inks disclosed in Patent Documents 3 to 4 have not been fully reviewed from the viewpoint of coating film formation on glass substrates. When these coatings are applied to glass substrates, there are coating liquids on the substrate. Poor coatability such as repellency, unevenness during drying of the coating film, and unevenness in the film thickness are problems in appearance.

The present invention was proposed in view of the conventional technical problems, and aims to provide a colored resin composition that suppresses repulsion or unevenness and can form a colored coating film with good appearance even when it is applied by spraying or inkjet.

The inventors of the present invention have intensively studied to solve the above-mentioned problems, and found that the above-mentioned problems can be solved by combining a specific surfactant.

That is, the object of the present invention is mainly achieved by the following configuration.

A coloring resin composition containing at least (A) coloring material, (B) binder resin, (C) organic solvent and two or more kinds of (D) surfactants, which contains (D1) Polyether modified silicone surfactants and (D2) silicon modified acrylic surfactants are used as the aforementioned surfactants. The total content of the aforementioned surfactants (D1) and (D2) is 200 ppm in the colored resin composition Above 1500ppm.

According to the present invention, even when coating by spraying or inkjet, repelling or unevenness can be suppressed, and a colored coating with good appearance can be formed. Furthermore, by using the colored resin composition of the present invention, a decorative substrate for a touch panel with a good appearance can be obtained.

[Form to implement the invention]

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

The coloring material resin composition system of the present invention is characterized by containing at least (A) coloring material, (B) binder resin, (C) organic solvent and two or more kinds of (D) surfactants, and contains (D1) polyether Modified silicone surfactants and (D2) silicon modified acrylic surfactants are used as surfactants. The total content of the aforementioned surfactants (D1) and (D2) is 200 ppm to 1500 ppm in the colored resin composition . (A) The coloring material has the function of coloring the resin composition, and (B) the binder resin has the function of holding each component of the colored resin composition. (C) Although the organic solvent has the function of uniformly dissolving or dispersing the (A) coloring material in the coloring resin composition, when the coloring film is formed from the coloring resin composition, it is easy to produce due to volatilization when the coating film is dried. The tendency to be uneven. Therefore, in the present invention, by containing the above-mentioned specific surfactant in a specific amount, even when the colored resin composition is sprayed or ink-jet coated on the substrate, it is possible to suppress repellency and other coating properties. Poor, suppress the unevenness of Benard cell when the coating film is dried, and form a colored film with good appearance.

(D1) The polyether-modified silicone surfactant system has the effect of reducing the interfacial tension of the colored resin composition on the substrate. Therefore, by containing (D1) a polyether-modified silicone-based surfactant, even when the colored resin composition is sprayed or ink-jet coated on the substrate, the coated liquid drops on the substrate It can also spread wet and can suppress poor coating properties such as repellency. However, in organic solvent-based coloring resin compositions, the surface tension reduction effect of the polyether-modified silicone-based surfactant is reduced, and when the coating film dries, it is easy to produce unevenness such as Benard cavitation. Subject. On the other hand, silicon-based surfactants or fluorine-based surfactants have the effect of reducing the surface tension of the colored resin composition, and can suppress unevenness during drying of the coating film. However, since the contact angle of the colored resin composition on the substrate becomes large, when the colored resin composition is sprayed or ink-jet applied to the substrate, there is a problem of repelling easily. Therefore, as a result of an in-depth review of a surfactant that can simultaneously suppress poor coatability when the colored resin composition is applied to a substrate by spraying or inkjet, and poor drying when the coating film is dried, it was found that the combination (D1) Polyether modified silicone surfactants and (D2) silicon modified acrylic surfactants can solve this problem. That is, by containing (D1) polyether-modified silicone surfactant, poor coating properties such as repellency can be suppressed, and by containing (D2) silicon-modified acrylic surfactant, it is possible to suppress The increase of the contact angle also reduces the surface tension, and can suppress the unevenness of the coating film drying.

(D1) Polyether-modified silicone-based surfactants include, for example, compounds having a structure represented by the following general formula (1).

In the above general formula (1), R ¹ represents a hydrogen atom or a methyl group. a represents an integer from 2 to 18, m represents an integer from -1 to 50, and n represents an integer from 1 to 8. In the case of m=-1, the general formula (1) is represented by the following general formula (2).

From the viewpoint of further reducing the interfacial tension of the colored resin composition on the glass substrate, the polyether chain is preferably longer. Therefore, a series of 5 or more is preferable, and 10 or more is more preferable. On the other hand, from the viewpoint of compatibility with other resins, a series of 18 or less is preferable. In addition, from the viewpoint of further reducing the surface tension of the colored resin composition, m is preferably 1 or more. On the other hand, from the viewpoint of further improving the interfacial tension on the glass substrate, m is preferably 10 or less, more preferably 5 or less, and more preferably 3 or less.

For (D1) polyether-modified silicone-based surfactants, commercially available ones can be used. For compounds having the structure represented by the aforementioned general formula (1), for example, "BYK" (registered Trademark)-345, "BYK"-346, "BYK"-347, "BYK"-348, "BYK"-349 (all manufactured by BYK-Chemie), "SILFACE" (registered trademark) SAG002, "SILFACE" SAG005, "SILFACE" SAG0503A, "SILFACE" SAG008 (all manufactured by Nissin Chemical Industry Co., Ltd.), etc. Two or more of these can be contained. Among these, "BYK"-347, "BYK"-348, "BYK"-349, etc., in which a in the aforementioned general formula (1) is 5 or more are particularly preferred.

(D2) Silicon-modified acrylic surfactants include, for example, compounds having a structure represented by the following general formula (3).

In the above general formula (3), R ² to R ⁴ each independently represent a hydrogen atom or a methyl group. b represents an integer from 1 to 18, p represents an integer from 0 to 50, and q represents an integer from 1 to 8. Preferably, b is an integer of 2-18.

For (D2) silicon-modified acrylic surfactants, commercially available ones can be used, and compounds having the structure represented by the aforementioned general formula (2) For example, "BYK"-3550, "BYK"-SILXLEAN3700 (all manufactured by BYK-Chemie), etc. can be mentioned. Two or more of these can be contained.

The total content of (D1) polyether-modified silicone-based surfactant and (D2) silicon-modified acrylic-based surfactant in the coloring resin composition of the present invention is 200 ppm to 1500 ppm in the coloring resin composition. When the total content of these components is less than 200 ppm, the contact angle of the colored resin composition increases due to the increase in the interfacial tension of the colored resin composition, and poor coating properties such as repelling are likely to occur. In addition, the surface tension of the colored resin composition increases. When the coating film dries, it becomes easy to produce unevenness such as Benard cavitation. The total content of these is preferably 300 ppm or more, and more preferably 400 ppm or more. On the other hand, when the total content of these exceeds 1500 ppm, the surface tension of the coating liquid is excessively lowered and uneven drying occurs. In addition, the surfactant bleeds out on the surface of the coating film, and the coating property or adhesion to the colored resin film is reduced. The total content of these is preferably 800 ppm or less.

The content of (D1) polyether-modified silicone surfactant in the coloring resin composition of the present invention is preferably 150 ppm or more and 1000 ppm or less in the coloring resin composition, and the contact angle can be easily adjusted to the preferable range described later .

The content of the (D2) silicon-modified acrylic surfactant in the colored resin composition of the present invention is preferably 200 ppm or more and 500 ppm or less in the colored resin composition. Since the surface tension is within the above range, the surface tension can be easily adjusted It is a preferable range described later.

From the viewpoint of further suppressing unevenness during drying of the coating film, the content of (D2) silicon-modified acrylic surfactant is relative to (D1) polyether-modified The ratio (D2)/(D1) of the content of the silicone-based surfactant is preferably 0.25 or more, more preferably 0.50 or more. On the other hand, from the viewpoint of further suppressing repulsion on the substrate, the (D2)/(D1) system is preferably 4.0 or less, and more preferably 2.0 or less.

(A) Coloring materials include, for example, organic pigments, inorganic pigments, and dyes. Two or more of these can be contained.

(dioxazine)系顏料；苝酮(perinone)系顏料；苝(perylene)系顏料；硫靛藍(thioindigo)系顏料；異吲哚啉系顏料；異吲哚啉酮系顏料；喹啉黃(quinophthalone)系顏料；士林(Suren)系顏料；金屬錯合物系顏料等。 As for organic pigments, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, bisazo, polyazo, etc.; copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine, etc. Phthalocyanine pigments; aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone (pyranthrone), violanthrone (violanthrone) and other anthraquinone pigments; quinacridone (quinacridone) pigments; double

(dioxazine) pigments; perinone pigments; perylene pigments; thioindigo pigments; isoindoline pigments; isoindolinone pigments; quinophthalone Pigments; Suren pigments; Metal complex pigments, etc.

As for inorganic pigments, for example, titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, aluminum white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, Iron red, molybdenum red, molybdenum orange, molybdenum chrome red, chrome yellow, cadmium yellow, yellow titanium oxide, titanium yellow, chromium oxide, chrome green, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine blue, iron blue , Cobalt Blue, Sky Blue, Cobalt Silica Blue, Cobalt Zinc Silica Blue, Manganese Violet, Cobalt Violet, etc.

The dyes include, for example, azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigo dyes, carbocation dyes, phthalocyanine dyes, methine, polymethine dyes, and the like.

When specific examples of representative pigments and dyes are represented by color index (CI) numbers, the following can be cited.

Examples of red pigments include pigment red (hereinafter abbreviated as PR) 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR192, PR209, PR215, PR216, PR217, PR220, PR223, PR224, PR226, PR227, PR228, PR240, PR254, etc.

Examples of orange pigments include pigment orange (hereinafter abbreviated as PO) 13, PO36, PO38, PO43, PO51, PO55, PO59, PO61, PO64, PO65, PO71, and the like.

Examples of yellow pigments include pigment yellow (hereinafter abbreviated as PY) PY12, PY13, PY17, PY20, PY24, PY83, PY86, PY93, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY138, PY139, PY147, PY148, PY150, PY153, PY154, PY166, PY168, PY185, etc.

In addition, examples of the purple pigments include pigment violet (hereinafter abbreviated as PV) 19, PV23, PV29, PV30, PV32, PV37, PV40, PV50, and the like.

In addition, as an example of a blue pigment, pigment blue (hereinafter abbreviated as PB) 15, PB15: 3, PB15: 4, PB15: 6, PB22, PB60, PB64, etc. can be used.

In addition, examples of green pigments include Pigment Green (hereinafter abbreviated as PG) 7, PG10, PG36, PG58, and the like.

Examples of black pigments include black organic pigments, mixed color organic pigments, inorganic pigments, and the like. As for black organic pigments, for example, carbon black, perylene black, aniline black and the like can be cited. As for the mixed-color organic pigment, for example, a combination of two or more red, blue, green, purple, yellow, magenta, and indigo (cyan) pigments to be pseudo-blackened can be mentioned. As for inorganic pigments, for example, graphite; metal particles of titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, etc.; oxides, composite oxides, sulfides, Nitride, oxynitride, etc. Among these, carbon black and titanium nitride are preferred because of their high light-shielding properties.

Examples of white pigments include titanium dioxide, barium carbonate, zirconium oxide, calcium carbonate, barium sulfate, aluminum white, and silicon dioxide.

Examples of dyes include, for example, CI Direct Red 2, 4, 9, 23, 26, 28, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 221, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247, CI Acid Red 35, 42, 51, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 145, 151, 154, 157, 158, 211, 249 , 254, 257, 261, 263, 266, 289, 299, 301, 305, 319, 336, 337, 361, 396, 397, CI Reactive Red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55, CI Basic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46, CI Direct Violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98 , 100, 101, CI acid violet 5, 9, 11, 34, 43, 47, 48, 51, 75, 90, 103, 126, CI active violet 1, 3, 4, 5, 6, 7, 8, 9 , 16, 17, 22, 23, 24, 26, 27, 33, 34, CI Basic Violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37 , 39, 40, 48, CI Direct Yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 142, 144, 161, 163, CI Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64 , 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195, 196, 197, 199, 218, 219, 222, 227, CI Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42, CI Basic Yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40, CI Acid Green 16, CI Acid Blue 9, 45, 80, 83, 90, 185, CI Basic Orange 21, 23, etc.

Examples of the binder resin (B) include epoxy resin, acrylic resin, silicone resin, polyimide resin, and the like. Two or more of these can be contained. Among these, acrylic resins and polyimide resins are preferred, which can improve the heat resistance of the coating film and the storage stability of the colored resin composition. In addition, from the viewpoint of easier pattern formation when forming patterns such as a black matrix, it is preferable to use an alkali-soluble resin.

The alkali-soluble resin in the present invention refers to a resin having one or more alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, and thiol groups. The alkali-soluble resin is preferably one having a carboxyl group, and a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound, or an acrylic resin having an ethylenically unsaturated group in the side chain is more preferred.

For unsaturated carboxylic acids, for example, monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinyl acetate; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid or their anhydrides, Polyvalent carboxylic acid monoesters such as phthalic acid mono(2-(meth)acryloxyethyl) ester, etc. Two or more of these can be used. Among these, acrylic acid and methacrylic acid are preferable from the viewpoint of sensitivity at the time of exposure and development.

As for ethylenically unsaturated compounds, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate Ester, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, secondary butyl acrylate, secondary butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, acrylic acid Tertiary butyl, tertiary butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, methyl Unsaturated carboxylic acid alkyl esters such as benzyl acrylate; aromatic vinyl groups such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, etc. Compounds; (cross-linked) cyclic hydrocarbon compounds such as tricyclodecyl (meth)acrylate; unsaturated carboxylic acid amino alkyl esters such as aminoethyl acrylate; glycidyl acrylate, methyl Acrylic ring Unsaturated glycidyl carboxylic acid such as oxypropyl ester; vinyl carboxylate such as vinyl acetate and vinyl propionate; vinyl cyanide compound such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile ; Aliphatic conjugated dienes such as 1,3-butadiene and isoprene; polystyrene, polymethyl acrylate, polymethyl methacrylate with acryloyl or methacryloyl groups at the end , Polybutyl acrylate, polybutyl methacrylate, etc. Two or more of these can be used. Among these, benzyl acrylate and benzyl methacrylate are preferable from the viewpoint of dispersion stability and pattern processability.

Examples of acrylic resins having ethylenically unsaturated groups in their side chains include copolymers described in Japanese Patent No. 3120476, Japanese Patent Laid-Open No. 8-262221, or commercially available acrylic resins that are photocurable "Cyclomer" (registered trademark) P" (Daicel Chemical Industry Co., Ltd.), alkali-soluble Cardo resin, etc.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, and more preferably 8,000 or more from the viewpoint of improving the photosensitivity. On the other hand, the Mw of the alkali-soluble resin is preferably 40,000 or less from the viewpoint of enhancing the solubility to ester solvents or alkali developing solutions and suppressing residues. Here, the weight average molecular weight of the alkali-soluble resin refers to a value measured by gel permeation chromatography using tetrahydrofuran as a carrier, and converted using a calibration line using standard polystyrene.

The acid value of the alkali-soluble resin is preferably 60-150 (mgKOH/g).

From the viewpoint of the coloring power of the coloring resin composition of the present invention and the coloring film obtained from the coloring resin composition, the content ratio of (A) coloring material to (B) binder resin (A)/(B)( Mass ratio), which is above 20/80 Above is better, more preferably 40/60 or more. On the other hand, from the viewpoint of the dispersion stability of (A) coloring material, the content ratio (A)/(B) (mass ratio) of (A) coloring material and (B) binder resin is 90/10 The following are better.

(C) Organic solvents include, for example, aliphatic hydrocarbons, carboxylic acid esters, ketones, ethers, and alcohols. Two or more of these can be contained. Among these, carboxylic acid esters, ketones, and ethers are preferred.

As for the carboxylic acid ester, for example, benzyl acetate, ethyl benzoate, γ-butyrolactone, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butanyl acetate Oxyethyl ester, 3-methoxy-3-methyl-butyl acetate, diethyl oxalate, ethyl acetate, cyclohexyl acetate, 3-methoxy-butyl acetate, ethyl Methyl acetate, ethyl-3-ethoxy propionate, 2-ethylbutyl acetate, isoamyl propionate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate , Amyl acetate, propylene glycol monomethyl ether acetate, etc.

Examples of ketones include cyclopentanone and cyclohexanone.

The ethers include, for example, aliphatic ethers such as propylene glycol derivatives such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, and dipropylene glycol monomethyl ether.

The alcohols include, for example, aliphatic alcohols such as butanol, 3-methyl-2-butanol, and 3-methyl-3-methoxybutanol.

Among these organic solvents, esters of saturated aliphatic carboxylic acids and saturated alcohols are preferred, 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, 3-methyl Acetate esters such as oxy-butyl acetate and propylene glycol monomethyl ether acetate; propionate esters such as propylene glycol monomethyl ether propionate are more preferred.

Examples of organic solvents other than the above include aliphatic esters such as ethyl acetate, butyl acetate, isoamyl acetate, xylene, ethylbenzene, solvent naphtha, and the like.

When applying the colored resin composition of the present invention to a curved substrate by spraying or inkjet, in order to appropriately adjust the volatility and drying characteristics, it is preferable to contain two or more (C) organic solvents. Specifically, an organic solvent having a boiling point of 150°C or higher and 230°C or lower under atmospheric pressure and an organic solvent having a boiling point of lower than 150°C under atmospheric pressure are preferably contained. From the viewpoint of suppressing aggregation of the (A) coloring material caused by the drying of the coating liquid in the nozzle, the boiling point at atmospheric pressure is 150°C or higher with 10 parts by mass or more relative to 100 parts by mass of the total organic solvent (C) Organic solvents below 230°C are preferred. On the other hand, from the viewpoint of suppressing the dripping of the coating liquid on the curved glass and making the film thickness more uniform, it contains 75 parts by mass or less of the boiling point at atmospheric pressure relative to 100 parts by mass of the total organic solvent (C) An organic solvent of 150°C or more and 230°C or less is preferable. The boiling point of an organic solvent with a boiling point of 150°C or more and 230°C or less under atmospheric pressure is more preferably 150°C or more and 200°C or less.

From the viewpoint of easier pattern formation when forming patterns such as a black matrix, it is preferable that the coloring resin composition of the present invention has photosensitivity, and it is preferable that it contains a reactive monomer and a photoradical polymerization initiator. .

As for the reactive monomers, monofunctional or polyfunctional acrylic monomers or acrylic oligomers can be cited. Two or more of these can be contained. Among these, multifunctional acrylic monomers are preferred.

As for the multifunctional acrylic monomers, for example, bisphenol A diglycidyl ether (meth)acrylate, poly(meth)acrylate urethane, modified bisphenol A epoxy (Meth)acrylate, 1,6-hexanediol (meth)acrylate adipic acid, anhydrous propylene oxide phthalate (meth)acrylate, diethylene glycol trimellitate (meth)acrylic acid Ester, rosin modified epoxy di(meth)acrylate, acid alcohol modified (meth)acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid Ester, bisphenol A diglycidyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, triacryl formal (triacryl formal) ), pentaerythritol tetra(meth)acrylate or its acid-modified body, dipentaerythritol hexa(meth)acrylate or its acid-modified body, dipentaerythritol penta(meth)acrylate or its acid-modified body, 2 ,2-bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]propane, bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]methane , Bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl] sulfide, bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]ether, 4 ,4'-bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]cyclohexane, 9,9-bis[4-(3-propenyloxy-2-hydroxypropane Oxy) phenyl] 茀, 9,9-bis[3-methyl-4-(3-propenyloxy-2-hydroxypropoxy) phenyl] 茀, 9,9-bis[3-chloro -4-(3-propenyloxy-2-hydroxypropoxy)phenyl] fen, bisphenoxyethanol fendiacrylate, bisphenoxyethanol fendimethacrylate, biscresol fendi Acrylate, biscresol dimethacrylate, etc. As the polyfunctional acrylic oligomer, the diacrylate oligomer described in Japanese Patent No. 3621533 or Japanese Patent Laid-Open No. 8-278630 can be cited.

Through the selection and combination of such multifunctional monomers or oligomers, the sensitivity or processability of the colored resin composition can be adjusted. In particular, in order to increase the sensitivity, it is preferable to have a functional group of 3 or more, more preferably a multifunctional acrylic monomer having 5 or more, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate or The acid-modified body is preferred. In addition, from the viewpoint of developability and processability, it is preferable to use a reaction product of an epoxy compound having two glycidyl ether groups and methacrylic acid and a polybasic acid carboxylic acid or its anhydride to obtain Alkali-soluble monomers containing unsaturated groups. In addition, from the viewpoint of the pattern shape at the time of development, a (meth)acrylate having a large amount of aromatic rings in the molecule and having a sulphur ring with high water repellency is preferred.

The content of the reactive monomer in the colored resin composition of the present invention is preferably 10 to 90 parts by mass relative to 100 parts by mass of the total content of (B) the binder resin and the reactive monomer.

Examples of the photoradical polymerization initiator include alkylphenone-based photoradical polymerization initiators or oxime ester-based photoradical polymerization initiators. Two or more of these can be contained.

(thioxanthone)系光自由基聚合起始劑、咪唑系光自由基聚合起始劑、苯并噻唑系光自由基聚合起始劑、苯并

唑系光自由基聚合起始劑、咔唑系光自由基聚合起始劑、三

系光自由基聚合起始劑、磷系光自由基聚合起始劑、酞酸酯等之無機系 光自由基聚合起始劑等。此等之中，由使感度提升的觀點，α-胺基烷基苯酮系光自由基聚合起始劑為較佳。就烷基苯酮系光自由基聚合起始劑而言，可列舉例如，2,2-二乙氧基苯乙酮、2-甲基-1-(4-甲基苯硫基)-2-

啉基丙烷-1-酮、為BASF公司製「Irgacure」(註冊商標)369的2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮、為BASF公司製「Irgacure」379的2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯基]-1-丁酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基丙烷-1-酮等。 As for the alkylphenone-based photoradical polymerization initiator, for example, α-aminoalkylphenone-based photoradical polymerization initiator, α-hydroxyalkylphenone-based photoradical polymerization initiator, Starter, benzophenone-based photo-radical polymerization initiator, 9-oxysulfur

(thioxanthone)-based photo-radical polymerization initiator, imidazole-based photo-radical polymerization initiator, benzothiazole-based photo-radical polymerization initiator, benzo

Azole-based photo-radical polymerization initiator, carbazole-based photo-radical polymerization initiator, three

It is a photo-radical polymerization initiator, a phosphor-based photo-radical polymerization initiator, an inorganic photo-radical polymerization initiator such as phthalate ester, etc. Among these, an α-aminoalkylphenone-based photoradical polymerization initiator is preferred from the viewpoint of improving sensitivity. Examples of alkylphenone-based photoradical polymerization initiators include 2,2-diethoxyacetophenone, 2-methyl-1-(4-methylphenylthio)-2 -

2-benzyl-2-dimethylamino-1-(4-

2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4) 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4) 2-(dimethylamino)-2-[(4-methylphenyl)methyl) of "Irgacure" 379 manufactured by BASF Corporation -

(Hydroxy)phenyl]-1-butanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, etc.

The oxime ester-based photoradical polymerization initiator is, for example, 1,2-octanedione of "Irgacure" OXE01 manufactured by BASF Corporation, 1-[4-(phenylthio)-2-(O -Benzoyl oxime)], the ethyl ketone of "Irgacure" OXE02 manufactured by BASF, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3- Base]-,1-(0-Acetyl oxime), "Adeka" (registered trademark) Optomer N-1818, N-1919, Adeka Cruise NCI-831, etc. manufactured by ADEKA (Stock).

系光自由基聚合起始劑、咪唑系光自由基聚合起始劑、苯并噻唑系光自由基聚合起始劑、苯并

唑系光自由基聚合起始劑、咔唑系光自由基聚合起始劑、三

系光自由基聚合起始劑、磷系光自由基聚合起始劑、酞酸酯等之無機系光自由基聚合起始劑等而言，可列舉例如，二苯基酮、N,N’-四乙基-4,4’-二胺基二苯基酮、4-甲氧基-4’-二甲基胺基二苯基酮、苯偶姻、苯偶姻甲基醚、苯偶姻異丁基醚、苄基二甲基縮酮、α-羥基異丁基 苯酮、9-氧硫

、2-氯9-氧硫

、t-丁基蒽醌、1-氯蒽醌、2,3-二氯蒽醌、3-氯-2-甲基蒽醌、2-乙基蒽醌、1,4-萘醌、9,10-菲醌、1,2-苯并蒽醌、1,4-二甲基蒽醌、2-苯基蒽醌、2-(o-氯苯基)-4,5-二苯基咪唑2量體、2-巰基苯并噻唑、2-巰基苯并

唑、4-(p-甲氧基苯基)-2,6-二-(三氯甲基)-s-三

等。 On the diphenyl ketone-based photo-radical polymerization initiator, 9-oxysulfur

-Based photo-radical polymerization initiator, imidazole-based photo-radical polymerization initiator, benzothiazole-based photo-radical polymerization initiator, benzo

Azole-based photo-radical polymerization initiator, carbazole-based photo-radical polymerization initiator, three

Inorganic photo-radical polymerization initiators such as photo-radical polymerization initiators, phosphor-based photo-radical polymerization initiators, phthalate esters, etc., for example, benzophenone, N,N'-Tetraethyl-4,4'-diaminobenzophenone,4-methoxy-4'-dimethylaminobenzophenone, benzoin, benzoin methyl ether, benzidine In-in-isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutyl phenone, 9-oxysulfur

, 2-Chloro 9-oxysulfur

, T-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9, 10-phenanthrenequinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-(o-chlorophenyl)-4,5-diphenylimidazole 2 Weight body, 2-mercaptobenzothiazole, 2-mercaptobenzo

Azole, 4-(p-methoxyphenyl)-2,6-bis-(trichloromethyl)-s-tri

Wait.

The content of the photo-radical polymerization initiator in the coloring resin composition of the present invention is preferably 1-20 parts by mass relative to 100 parts by mass of the total content of the binder resin and reactive monomer (B).

It is preferable that the colored resin composition of the present invention contains a polymer dispersant, so that the (A) coloring material can be uniformly and stably dispersed in the colored resin composition. As for polymer dispersants, for example, polyester polymer dispersants, acrylic polymer dispersants, polyurethane polymer dispersants, polyallylamine polymer dispersants, carbon dioxide Imine-based dispersants, etc. Two or more of these can be contained. The polymer dispersant can be appropriately selected according to the type of (A) coloring material.

As for polymer dispersants, there are dispersants with only amine values, dispersants with only acid values, dispersants with amine values and acid values, and various dispersants with neither amine nor acid values. In order to make the effect of the present invention remarkable, it is preferable to use a dispersant having an amine value, and a polymer dispersant having only an amine value is preferable. The amine value of the polymer dispersant is preferably 10 or more and 100 or less, and more preferably 10 or more and 60 or less.

Specific examples of dispersants having only amine values include DISPERBYK 102, DISPERBYK 160, DISPERBYK 161, DISPERBYK 162, DISPERBYK 2163, DISPERBYK 2164, DISPERBYK 166, DISPERBYK 167, DISPERBYK 168, DISPERBYK 2000, DISPERBYK 2050, DISPERBYK 2150, DISPERBYK 2155, DISPERBYK LPN6919, DISPERBYK LPN21116, DISPERBYK LPN21234, DISPERBYK 9075, DISPERBYK 9077 4015, BYKA Chemie; EFKA 4020, EFKA 4046, EFKA 4047, EFKA 4050, EFKA 4055, EFKA 4060, EFKA 4080, EFKA 4300, EFKA 4330, EFKA 4340, EFKA 4400, EFKA 4401, EFKA 4402, EFKA 4403, EFKA 4800 (above, manufactured by BASF ); AJISPER PB711 (Ajinomoto Fine-Techno (stock) system), etc.

Among dispersants having only amine valence, dispersants having at least a tertiary amine group are more preferable. Specific examples include DISPERBYK LPN6919, DISPERBYK LPN21116, and the like.

Specific examples of polymer dispersants having amine and acid values include DISPERBYK 142, DISPERBYK 145, DISPERBYK 2001, DISPERBYK 2010, DISPERBYK 2020, DISPERBYK 2025, DISPERBYK 9076, Anti-Terra-205 (above, BYK -Chemie Corporation); Solsperse 24000 (Lubrizol Corporation); AJISPER PB821, AJISPER PB880, AJISPER PB881 (above, Ajinomoto Fine-Techno Corporation), etc.

From the viewpoint of making the (A) coloring material more stable and dispersing, relative to the content of (A) coloring material 100 parts by mass, the content of the polymer dispersant in the coloring resin composition of the present invention is 1 part by mass or more. Good, 3 More parts by mass is better. On the other hand, when the coloring resin composition of the present invention has photosensitivity, from the viewpoint of photosensitivity, the content of the polymer dispersant is preferably 50 parts by mass or less relative to 100 parts by mass of the coloring material (A) , 30 parts by mass or less is more preferable.

The colored resin composition of the present invention may contain (D) surfactants other than the aforementioned (D1) and (D2), which can further suppress unevenness during drying and improve the flatness of the colored film. Regarding (D) surfactants other than the aforementioned (D1) and (D2), for example, anionic surfactants such as ammonium lauryl sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, etc.; stearylamine Cationic surfactants such as acetate, lauryl trimethyl ammonium chloride; amphoteric surfactants such as lauryl dimethyl amine oxide, lauryl carboxymethyl hydroxyethyl imidazolium betaine, etc.; polyoxyethylene laurel Non-ionic surfactants such as polyoxyethylene stearyl ether, sorbitan monostearate, etc.; silicone-based surfactants with polydimethylsiloxane as the main skeleton; fluorine Series surfactants; acrylic surfactants, etc.

When (D) surfactants other than (D1) and (D2) are contained, the content is preferably in a range that does not inhibit the effects of (D1) and (D2). Specifically, the colored resin composition is less than 1000 ppm It is preferable, and 500 ppm or less is more preferable.

The photosensitive colored resin composition of the present invention preferably contains an adhesion modifier such as a silane coupling agent, which can improve the adhesion between the coating film and the base substrate. The silane coupling agent includes a silane coupling agent having a functional group such as a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, and an amino group. Specifically, 3-glycidoxy Propyl trimethoxy silane, 3-glycidoxy propyl triethoxy silane, 3-glycidoxy propyl methyl dimethoxy silane, 3-glycidoxy propyl methyl Diethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, ethylene Trimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethyl Oxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethyl Oxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) Propylamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, etc. are preferred.

From the viewpoint of further improving adhesion, the content of the adhesion modifier in the colored resin composition of the present invention is based on the solid content of the colored resin composition, namely (A) coloring material, (B) binder resin, and Among the total 100% by mass of the additives, 1% by mass or more is preferable, and 2% by mass or more is more preferable. On the other hand, when the colored resin composition of the present invention has photosensitivity, from the viewpoint of improving the resolution of the pattern by alkali development, the content of the adhesion modifier is 15% by mass in the solid content of the colored resin composition. % Or less is preferable, and 10 mass% or less is more preferable.

From the viewpoint of productivity, the solid content concentration in the colored resin composition of the present invention is preferably 2% by mass or more, and more preferably 5% by mass or more. On the other hand, from the viewpoint of dispersion stability, the solid content concentration of the colored resin composition is preferably 60% by mass or less, and more preferably 30% by mass or less.

The surface tension of the colored resin composition of the present invention at 25°C, from the viewpoint of further suppressing the thinning of the end of the coating film after drying, is preferably 24 mN/m or more, and more preferably 25 mN/m or more . On the other hand, the surface tension at 25°C of the colored resin composition of the present invention is preferably 28 mN/m or less, and more preferably 27.5 mN/m or less from the viewpoint of further suppressing uneven drying. In addition, the surface tension is a value measured at 25°C using a platinum plate by the Wilhelmy method (platinum plate method, vertical plate method). The surface tension of the colored resin composition of the present invention at 25°C can be adjusted by, for example, the content of the (D2) silicon-modified acrylic surfactant. As for the method of taking the surface tension within the above range, for example, For example, the content of (D2) silicon-modified acrylic surfactant is adopted in the aforementioned preferred range.

The contact angle on the alkali-free glass of the colored resin composition of the present invention is preferably 1° or more from the viewpoint of making the film thickness at the end of the substrate more uniform. On the other hand, when the colored resin composition of the present invention is coated on a substrate by spraying or inkjet, the smaller the contact angle, the easier it is to combine the falling droplets, and the generation of uncoated areas can be suppressed. Therefore, the contact angle on the alkali-free glass of the colored resin composition of the present invention is preferably 13° or less, more preferably 12° or less, and even more preferably 11° or less. In addition, the contact angle is a value measured by dropping the colored resin composition onto an alkali-free glass (# 1737, manufactured by Corning Corporation) washed with an alkaline detergent and using a portable contact angle meter. The contact angle on the alkali-free glass of the colored resin composition of the present invention can be adjusted by, for example, the content of (D1) polyether-modified silicone-based surfactant, and the contact angle can be adjusted to the above range For example, a method of setting the content of (D1) polyether-modified silicone-based surfactant into the aforementioned preferable range can be mentioned.

The viscosity of the colored resin composition of the present invention at 25°C is 2mPa‧s from the viewpoint of suppressing the flow of the coating liquid and making the film thickness more uniform when the colored resin composition is applied to a substrate with an inclination The above is preferable, and 3mPa‧s or more is more preferable. On the other hand, the viscosity of the colored resin composition of the present invention at 25° C., when the colored resin composition of the present invention is coated on a substrate by spraying or inkjet, is easy to fall due to the flow of droplets In terms of droplet bonding, from the viewpoint of suppressing the generation of uncoated areas, 20 mPa·s or less is preferable, and 15 mPa·s or less is more preferable. In addition, the viscosity is a value measured at 100 rpm with a portable viscometer set at 25.0±0.2°C.

Next, the manufacturing method of the colored resin composition of the present invention will be explained. Generally, a dispersing machine is used to disperse (A) coloring material in a resin solution containing (B) binder resin and (C) organic solvent. In the obtained dispersion, add (D) surfactant and if necessary Methods of other ingredients. From the viewpoint of dispersion stability, it is better to blend 5-50 parts by mass of (B) binder resin relative to 100 parts by mass of (A) coloring material, and it is more preferable to blend 7-40 parts by mass good.

Examples of the dispersing machine include a ball mill, a sand mill, a three-roll mill, and a high-speed impact mill. From the viewpoint of dispersion efficiency and microdispersion, a bead mill is preferred. As for the bead mill, a co-ball mill, a basket mill, a pin mill, a horizontal sand mill (Dyno-mill), etc. can be mentioned.

As for the beads of the bead mill, titanium oxide beads, zirconia beads, zircon beads, and the like can be cited. The diameter of the beads is preferably 0.01 mm or more and 5.0 mm or less, and more preferably 0.03 mm or more and 1.0 mm or less. (A) When the primary particle diameter of the coloring material and the secondary particle formed by agglomeration of the primary particles have a small particle diameter, it is preferable to use finely dispersed beads with a bead diameter of 0.03 mm or more and 0.10 mm or less. In this case, it is better to use a bead mill with spacers that can separate the fine dispersion beads from the dispersion liquid by centrifugal separation. On the other hand, when dispersing the (A) coloring material containing submicron coarse particles, it is better to use dispersed beads of 0.10 mm or more. With a higher crushing force, the (A) coloring material can be Disperse more finely.

By hardening the colored resin composition of the present invention, the colored coating film of the present invention can be obtained. Regarding the method of forming a colored coating film from the colored resin composition, a colored resin composition having negative photosensitivity will be described as an example.

The photosensitive colored resin composition is applied on a substrate to obtain a coating film. As for the substrate, for example, transparent substrates such as soda glass, alkali-free glass, quartz glass, silicon wafers, ceramic substrates, and gallium arsenide substrates can be cited. The coating method includes, for example, spin coating using a spinner, spray coating, inkjet coating, die coating, roll coating, etc. In the present invention, spray coating and inkjet coating are preferred. The thickness of the coating film can be appropriately selected by the coating method or the like. Usually the film thickness after drying is made 1~150μm.

The obtained coating film is dried to obtain a dry film. The drying method includes, for example, heat drying, air drying, drying under reduced pressure, and infrared irradiation. Examples of the heating and drying device include an oven and a hot plate. The drying temperature is preferably 50 to 150°C, and the drying time is preferably 1 minute to several hours.

For the obtained dry film, a mask having a desired pattern is interposed, and chemical rays are irradiated to obtain an exposed film. The chemical rays to be irradiated include, for example, ultraviolet rays, visible rays, electron beams, and X-rays. For the colored resin composition of the present invention, it is preferable to irradiate the i-ray (365nm), h-ray (405nm), and g-ray (436nm) of a mercury lamp.

啉等之環狀胺類等之有機鹼類。 The unexposed portion is removed by developing the obtained exposed film using an alkaline developer or the like, and a pattern is obtained. As for the alkaline compound used in the alkaline developer, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, ammonia water, etc.; ethyl Primary amines such as amine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine ; Tetramethylammonium hydroxide (TMAH) and other tetraalkylammonium hydroxides, choline and other quaternary ammonium salts; triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylamino Alcohol amines such as ethanol; pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]- 5-nonane,

Organic bases such as cyclic amines such as morpholines.

The concentration of the alkaline compound in the alkaline developer is usually 0.01-50% by mass, preferably 0.02-1% by mass. In addition, in order to make the pattern shape after development better, a surfactant such as a nonionic surfactant can be added in an amount of 0.1 to 5% by mass. Furthermore, when the developer is an alkaline aqueous solution, a water-soluble organic solvent such as ethanol, γ-butyrolactone, dimethylformamide, and N-methyl-2-pyrrolidone can be added to the developer.

The development method includes, for example, a dipping method, a spraying method, and a liquid coating method. The obtained pattern can also be rinsed with pure water or the like.

By performing heat treatment (post-baking) on the obtained pattern, a patterned colored film can be obtained. The heat treatment can be performed in any of air, nitrogen atmosphere, and vacuum state. The heating temperature is preferably 150 to 300°C, and the heating time is preferably 0.25 to 5 hours. The heating temperature can be changed continuously or in stages.

When the colored resin composition of the present invention contains a black (A) coloring material, the colored resin composition can be preferably used for light-shielding images and organic light-shielding images such as black substrates of color filters and the like provided in liquid crystal display devices. The formation of the colored partition wall inside the EL display and the colored film on the decorative substrate of the touch panel.

The decorative substrate for the touch panel of the present invention preferably has the aforementioned colored film, transparent electrode, transparent insulating film and protective film on the transparent substrate. In addition, the formation of each film can be performed by, for example, the method described in JP 2009-301767 A.

[Example]

Hereinafter, examples and comparative examples are used to describe the present invention in further detail, but the present invention is not limited to the following examples.

<Evaluation method>

"Surface Tension"

With respect to the photosensitive black resin composition obtained in each of the Examples and Comparative Examples, the surface tension was measured at 25°C using an automatic surface tension meter K11 (manufactured by KRUSS Corporation) and a platinum plate.

"Contact angle"

Drop it on the alkali-free glass (# 1737, manufactured by Corning) cleaned with alkaline detergent (Haemosol HEM026-058 (manufactured by Hekenyao Co., Ltd.)) The photosensitive black resin composition obtained in each Example and Comparative Example was measured for contact angle using a portable contact angle meter PCA-1 (manufactured by Kyowa Interface Science Co., Ltd.).

"Viscosity"

For the photosensitive black resin composition obtained in each of the Examples and Comparative Examples, the viscosity at 100 rpm was measured using a viscometer (RE105L manufactured by Toki Sangyo Co., Ltd.) whose temperature was set to 25.0±0.2°C.

"Coating Rejection"

The prebaked films obtained in the respective Examples and Comparative Examples were visually observed under a halogen spotlight with an illuminance of 50,000 lm/m ² , and the presence or absence of coating rejection was evaluated using the following criteria. From the viewpoint of industrial use, A and B were judged to be acceptable.

A: In the state where the lamp is lit from the substrate, no light leakage is observed.

B: Although there is no uncoated area on the substrate, light leakage is observed in the state where the lamp is lit from under the substrate.

C: There is an uncoated area on the substrate.

"Uneven dryness"

The pre-baked films obtained in the respective examples and comparative examples were visually observed under a fluorescent lamp and under a Na lamp, and the presence or absence of uneven drying was evaluated according to the following criteria. From the viewpoint of industrial use, A and B were judged to be acceptable.

A: The coating film was observed under fluorescent lamp and Na lamp, and no unevenness was confirmed.

B: Observation of the coating film under a fluorescent lamp, although no unevenness was confirmed, but observation of the coating film under a Na lamp, confirmed that there was an unevenness.

C: Observation of the coating film under fluorescent light to confirm that there is unevenness.

<Synthesis of acrylic polymer>

[Synthesis Example 1]

According to the method described in Example 1 of Japanese Patent No. 3120476, after synthesizing methyl methacrylate/methacrylic acid/styrene copolymer (weight composition ratio 30/40/30), add epoxy propyl methyl Acrylic polymer (P-1) powder having the characteristics of an average molecular weight (Mw) of 20,000 and an acid value of 110 (mgKOH/g) was obtained by reprecipitating with pure water, filtering, and drying 40 parts by weight of the base acrylate.

<Production of photosensitive colored resin composition>

[Example 1]

氧化鋯珠(大研化學工業(股)製、YTZ BALL)的離心分離隔片的Ultra Apex Mill(壽工業(股)製)，以回轉速度8m/s進行3小時分散，獲得固體含量濃度25重量%、著色材/樹脂(重量比)=70/30之黑色分散液1。 175 g of high-resistance carbon black TPK1227R (manufactured by Cabot), 171 g of a 35% by weight solution of propylene glycol monoethyl ether acetate of acrylic polymer (P-1), and DISPERBYK LPN-21116 (BYK) as a polymer dispersant -38 g of propylene glycol monoethyl ether acetate (40% by weight solution) manufactured by Chemie, and 616 g of propylene glycol monoethyl ether acetate (PMA) were added to the tank, and stirred with a homogenizer (manufactured by Primix) for 20 minutes to obtain preliminary dispersion liquid. After that, the pre-dispersion is supplied to 0.05mm with 75% filling

Ultra Apex Mill (manufactured by Kotobukiya Co., Ltd.) of the centrifugal separator of zirconia beads (manufactured by Daiken Chemical Industry Co., Ltd., YTZ BALL) was dispersed at a rotation speed of 8 m/s for 3 hours to obtain a solid content concentration of 25 Weight%, coloring material/resin (weight ratio)=70/30 black dispersion liquid 1.

Mix 301.94g of this black dispersion 1, 185.17g of acrylic polymer (P-1) 35% by weight solution of propylene glycol monoethyl ether acetate, 407.79g of propylene glycol monoethyl ether acetate, and 40.00g of 3-methyl Oxy-3- Methyl butanol (MMB), 3.91g of "Adeka" (registered trademark) Optomer NCI-831 (made by ADEKA (stock)), 6.52g of "Irgacure" (registered trademark) 379 (made by BASF), 45.67g Pentaerythritol hexaacrylate (DHPA manufactured by Nippon Kayaku Co., Ltd.), 3.00g of 3-propenoxypropyltrimethoxysilane, 3.00g of polyether modified silicone surfactant BYK348 (BYK-Chemie) Prepared) 10% by weight solution of propylene glycol monoethyl ketone acetate and 3.00g of 10% by weight solution of propylene glycol monoethyl ether acetate of silicon-modified acrylic surfactant BYK3550 (manufactured by BYK-Chemie) Sexual black resin composition Bk-1. According to the evaluation results of the aforementioned method, the surface tension of the photosensitive black resin composition Bk-1 is 26.8 mN/m, the contact angle is 9.8°, and the viscosity is 5.6 mPa·s.

On an alkali-free glass (Corning "1737" material) substrate, the obtained photosensitive black resin composition Bk-1 was sprayed and coated with a spray coater (Asahi Sunac Co., Ltd., rotary atomizing nozzle) at a spraying distance of 50 mm , Spraying air pressure 0.1MPa, discharge volume 10g/min, nozzle speed 30m/min, recoating interval 10mm, after coating, pre-bake in a hot air oven at 90℃ for 10 minutes. As a result of evaluation of this prebaked film by the aforementioned method, a film with good appearance without coating rejection or uneven drying was obtained.

After that, the exposure machine "XG-5000" manufactured by Dainippon Crein Co., Ltd. was used for exposure through a gray tone mask, and development was performed using a 0.045 mass% potassium hydroxide aqueous solution. Furthermore, it was cured at 230°C for 30 minutes. In this way, a black light-shielding film BM-1 with a thickness of 3.0 μm was produced.

[Example 2]

In addition to the polyether-modified silicone-based surfactant BYK348 (manufactured by BYK-Chemie), the addition amount of propylene glycol monoethyl ether acetate 10% by weight solution was made 4.00g and the silicon-modified acrylic surfactant BYK3550 Except that the addition amount of the 10% by weight solution of propylene glycol monoethyl ether acetate (manufactured by BYK-Chemie) was set to 2.00 g, the photosensitive black resin composition Bk-2 was prepared in the same manner as in Example 1. The photosensitive black resin composition Bk-2 has a surface tension of 27.2mN/m, a contact angle of 9.2°, and a viscosity of 5.6mPa‧s.

Using the photosensitive black resin composition Bk-2, a prebaked film was produced in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Example 3]

In addition to the polyether-modified silicone-based surfactant BYK348 (manufactured by BYK-Chemie), the addition amount of the 10% by weight solution of propylene glycol monoethyl ether acetate is made 1.50g and the silicon-modified acrylic surfactant BYK3550 Except that the addition amount of the 10% by weight solution of propylene glycol monoethyl ether acetate (manufactured by BYK-Chemie) was set to 1.50 g, the photosensitive black resin composition Bk-3 was prepared in the same manner as in Example 1. The photosensitive black resin composition Bk-3 has a surface tension of 27.6mN/m, a contact angle of 11.7°, and a viscosity of 5.6mPa‧s.

Using the photosensitive black resin composition Bk-3, a prebaked film was produced in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Example 4]

In addition to the polyether modified silicone surfactant BYK348 (manufactured by BYK-Chemie), propylene glycol monoethyl ether acetate The addition amount of 10% by weight solution was made 6.00g and the addition amount of propylene glycol monoethyl ether acetate 10% by weight solution of the silicon-modified acrylic surfactant BYK3550 (manufactured by BYK-Chemie) was made 6.00g. In the same manner as in Example 1, a photosensitive black resin composition Bk-4 was prepared. The photosensitive black resin composition Bk-4 has a surface tension of 24.8mN/m, a contact angle of 8.2°, and a viscosity of 5.6mPa‧s.

Using the photosensitive black resin composition Bk-4, a prebaked film was produced in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Example 5]

In addition to the polyether-modified silicone-based surfactant BYK348 (manufactured by BYK-Chemie), the addition amount of the 10% by weight solution of propylene glycol monoethyl ether acetate is made 4.00g and the silicon-modified acrylic surfactant BYK3550 The addition amount of 10% by weight solution of propylene glycol monoethyl ether acetate (manufactured by BYK-Chemie) was made 2.00g, and 1.00g of propylene glycol monoethyl ether of silicon-based surfactant BYK333 (manufactured by BYK-Chemie) was further added Except for the 10% by weight acetate solution, the photosensitive black resin composition Bk-5 was prepared in the same manner as in Example 1. The photosensitive black resin composition Bk-5 has a surface tension of 26.8mN/m, a contact angle of 11.5°, and a viscosity of 5.6mPa‧s.

Using the photosensitive black resin composition Bk-5, a prebaked film was produced in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Example 6]

Except that the addition amount of the 10% by weight solution of propylene glycol monoethyl ether acetate of the polyether-modified silicone-based surfactant BYK348 (manufactured by BYK-Chemie) is set to 5.00g, and the silicone-modified acrylic Except that the addition amount of the 10% by weight solution of propylene glycol monoethyl ether acetate of the surfactant BYK 3550 (manufactured by BYK-Chemie) was set to 1.00 g, in the same manner as in Example 1, a photosensitive black resin composition Bk-6 was prepared. The photosensitive black resin composition Bk-6 has a surface tension of 27.8mN/m, a contact angle of 8.6°, and a viscosity of 5.6mPa‧s.

Using the photosensitive black resin composition Bk-6, a prebaked film was produced in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Example 7]

In addition to the polyether-modified silicone-based surfactant BYK348 (manufactured by BYK-Chemie), the addition amount of a 10% by weight solution of propylene glycol monoethyl ether acetate is made 1.00g, and the silicon-modified acrylic surfactant A photosensitive black resin composition Bk-7 was prepared in the same manner as in Example 1, except that the addition amount of the 10% by weight solution of propylene glycol monoethyl ether acetate of BYK 3550 (manufactured by BYK-Chemie) was set to 5.00 g. The photosensitive black resin composition Bk-7 has a surface tension of 25.7mN/m, a contact angle of 12.1°, and a viscosity of 5.6mPa‧s.

Using the photosensitive black resin composition Bk-7, a prebaked film was produced in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Example 8]

Except that BYK347 (manufactured by BYK-Chemie) 10% by weight solution of propylene glycol monoethyl ether acetate was used instead of BYK348 as the polyether-modified silicone-based surfactant, the photosensitivity was prepared in the same manner as in Example 2. Black resin composition Bk-8. The photosensitive black resin composition Bk-8 has a surface tension of 27.0mN/m, a contact angle of 10.2°, and a viscosity of 5.6mPa‧s.

Using the photosensitive black resin composition Bk-8, a prebaked film was produced in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Example 9]

Except that BYK349 (manufactured by BYK-Chemie) 10% by weight solution of propylene glycol monoethyl ether acetate was used instead of BYK348 as a polyether-modified silicone-based surfactant, the photosensitivity was prepared in the same manner as in Example 2. Black resin composition Bk-9. The photosensitive black resin composition Bk-9 has a surface tension of 27.4mN/m, a contact angle of 9.6°, and a viscosity of 5.6mPa‧s.

Using the photosensitive black resin composition Bk-9, a prebaked film was produced in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Example 10]

Except for using SILFACESAG503A (manufactured by Nissin Chemical Industry Co., Ltd.) 10% by weight solution of propylene glycol monoethyl ether acetate instead of BYK348 as a polyether-modified silicone-based surfactant, it is the same as in Example 2. The photosensitive black resin composition Bk-10 was prepared. The photosensitive black resin composition Bk-10 has a surface tension of 27.0mN/m, a contact angle of 8.8°, and a viscosity of 5.6mPa‧s.

Using the photosensitive black resin composition Bk-10, a prebaked film was produced in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Comparative Example 1]

In addition to adding 3.00g of silicon-based surfactant BYK333 (manufactured by BYK-Chemie), a 10% by weight solution of propylene glycol monoethyl ether acetate instead of polyether-modified silicone-based surfactant BYK348 (manufactured by BYK-Chemie) And silicon modified acrylic interface Except for the sexual agent BYK3550 (manufactured by BYK-Chemie), it was prepared in the same manner as in Example 1. The photosensitive black resin composition Bk-11. The photosensitive black resin composition Bk-11 has a surface tension of 26.0mN/m, a contact angle of 14.2°, and a viscosity of 5.6mPa‧s.

Using the photosensitive black resin composition Bk-11, a prebaked film was produced in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Comparative Example 2]

In addition to adding 3.00g of fluorine-based surfactant F-477 (manufactured by DIC), a 10% by weight solution of propylene glycol monoethyl ether acetate instead of polyketone-modified silicone-based surfactant BYK348 (BYK-Chemie) (Manufactured by) and silicon-modified acrylic surfactant BYK3550 (manufactured by BYK-Chemie), in the same manner as in Example 1, a photosensitive black resin composition Bk-12 was prepared. The photosensitive black resin composition Bk-12 has a surface tension of 26.4mN/m, a contact angle of 13.7°, and a viscosity of 5.6mPa‧s.

Using the photosensitive black resin composition Bk-12, a prebaked film was produced in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Comparative Example 3]

Except that the addition amount of the 10% by weight solution of propylene glycol monoethyl ether acetate of the polyether-modified silicone-based surfactant BYK348 (manufactured by BYK-Chemie) is set to 3.00g, no silicon-modified acrylic interface activity is added. Except for the agent BYK 3550 (manufactured by BYK-Chemie), in the same manner as in Example 1, a photosensitive black resin composition Bk-13 was prepared. The surface tension of the photosensitive black resin composition Bk-13 is 28.4mN/m, the contact angle is 8.8°, and the viscosity is 5.6mPa‧s.

Using the photosensitive black resin composition Bk-13, a prebaked film was produced in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Comparative Example 4]

Except for propylene glycol monoethyl ether acetate 10 without polyether modified silicone surfactant BYK348 (manufactured by BYK-Chemie) and silicon modified acrylic surfactant BYK3550 (manufactured by BYK-Chemie) Except that the addition amount of the weight% solution was set to 3.00 g, in the same manner as in Example 1, a photosensitive black resin composition Bk-14 was prepared. The photosensitive black resin composition Bk-14 has a surface tension of 26.8mN/m, a contact angle of 13.2°, and a viscosity of 5.6mPa‧s.

Using the photosensitive black resin composition Bk-14, a prebaked film was produced in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Comparative Example 5]

In addition to the addition of the 10% by weight solution of propylene glycol monoethyl ether acetate of the polyether-modified silicone-based surfactant BYK348 (manufactured by BYK-Chemie) to 0.50 g, and the silicone-modified acrylic interface activity Except that the addition amount of the 10% by weight solution of propylene glycol monoethyl ether acetate of the agent BYK 3550 (manufactured by BYK-Chemie) was set to 1.00 g, the photosensitive black resin composition Bk-15 was prepared in the same manner as in Example 1. In addition, the photosensitive black resin composition Bk-15 has a surface tension of 28.2 mN/m, a contact angle of 13.1°, and a viscosity of 5.6 mPa·s.

Using the photosensitive black resin composition Bk-15, a prebaked film was produced in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Comparative Example 6]

In addition to the polyether modified silicone surfactant BYK348 (manufactured by BYK-Chemie), the addition amount of the 10% by weight solution of propylene glycol monoethyl ether acetate is made 6.00g, and the silicon modified acrylic surfactant A photosensitive black resin composition Bk-16 was prepared in the same manner as in Example 1, except that the addition amount of the 10% by weight solution of propylene glycol monoethyl ether acetate of BYK 3550 (manufactured by BYK-Chemie) was set to 12.00 g. In addition, the photosensitive black resin composition Bk-16 has a surface tension of 23.7 mN/m, a contact angle of 7.6°, and a viscosity of 5.6 mPa·s.

Using the photosensitive black resin composition Bk-16, a prebaked film was produced in the same manner as in Example 1, and the evaluation results are shown in Table 1.

It is understood that the photosensitive black resin composition produced in the example has a good appearance when forming a dry film on a glass substrate by spray coating, repulsion or unevenness is suppressed.

[Possibility of industrial use]

The colored resin composition system of the present invention can easily provide a colored coating film that suppresses repulsion or unevenness and has a good appearance even when it is applied on a substrate by spraying or inkjet. Accordingly, it becomes possible to form high-performance color filter substrates or decorative substrates for liquid crystal display devices, decorative substrates for touch panels, colored partition walls and decorative film substrates for organic EL displays, etc., with high production efficiency. Coloring pattern.

Claims (9)

A coloring resin composition containing at least (A) coloring material, (B) binder resin, (C) organic solvent and two or more kinds of (D) surfactants, which contains (D1) Polyether modified silicone surfactants and (D2) silicon modified acrylic surfactants are used as the aforementioned surfactants. The total content of the aforementioned surfactants (D1) and (D2) is 200 ppm in the colored resin composition Above 1500ppm. The colored resin composition of claim 1, wherein the ratio (D2)/(D1) of the content of the aforementioned surfactant (D2) to the content of the aforementioned surfactant (D1) is 0.25 or more and 4.0 or less. For example, the colored resin composition of claim 1 or 2 has a surface tension of 24 mN/m or more and 28 mN/m or less at 25°C. For example, the colored resin composition of claim 1 or 2 has a contact angle of 1° or more and 13° or less on the alkali-free glass. For example, the colored resin composition of claim 1 or 2 has a viscosity at 25°C of 2mPa‧s or more and 20mPa‧s or less. The colored resin composition of claim 1 or 2, which contains at least carbon black and/or titanium nitride as the coloring material (A). Such as the colored resin composition of claim 1 or 2, which further contains a multifunctional acrylic monomer and a photo-radical polymerization initiator. A colored coating film comprising the colored resin composition according to any one of claims 1 to 7. A decorative substrate for a touch panel, which has a colored coating film as claimed in claim 8.