KR102548098B1 - colored resin composition - Google Patents

Abstract

An object of the present invention is to provide a colored resin composition capable of forming a colored film with good appearance while suppressing unevenness and unevenness even when applied by spray or inkjet. The present invention is a colored resin composition containing at least (A) a coloring agent, (B) a binder resin, (C) an organic solvent and two or more (D) surfactants, as the surfactant (D1) polyether-modified siloxane-based It is a colored resin composition containing a surfactant and (D2) a silicone-modified acrylic surfactant, and the total content of the surfactants (D1) and (D2) is 200 ppm or more and 1500 ppm or less in the colored resin composition.

Description

colored resin composition

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

Conventionally, it is common for a touch panel device to be mounted on the front surface of a display panel such as a liquid crystal display device, and a configuration in which a cover glass formed with a light shielding film by printing a black ink composition is pasted on the front surface of the touch panel has been common. However, such an exterior type touch panel configuration has a problem of increasing thickness and weight.

Therefore, recently, as a display device having a touch sensor function, a cover glass integrated touch panel in which a conductive film and a sensor are directly formed on a cover glass and a single sheet of glass serves as both the cover glass and the touch sensor has been proposed. In such a cover glass-integrated touch panel, a light blocking layer is formed on the glass, and a conductive film or wiring such as ITO is formed on the light blocking layer. As a manufacturing method of a touch panel integrated with cover glass, for example, a step of forming and polishing a light-shielding material on a glass substrate by a screen printing method, a step of applying an overcoat layer on the glass substrate, and a touch panel on the overcoat layer A method including a process of forming a sensor and a process of cutting a glass substrate for each touch panel sensor has been proposed (for example, see Patent Document 1). In addition, as a black composition suitable for decorating such a touch panel, a black composition containing at least two or more kinds of organic pigments, a binder resin, a silane coupling agent, and a photopolymerizable monomer has been proposed (see, for example, Patent Document 2).

However, in such a manufacturing method, there was a problem that the strength of the glass was insufficient. Then, examination of forming a cover-glass integral|integrated touchscreen is made|formed using the glass which cut into pieces and chemically strengthened. In addition, for the purpose of improving the designability, examination of forming a cover glass-integrated touch panel using curved glass is also being made.

It is difficult from the viewpoint of productivity to apply the conventional method of applying a light-shielding material by a slit coater or spinner to broken glass or curved glass, and inkjet or spray coating can be used as an alternative method.

On the other hand, studies on resin compositions suitable for inkjet coating have been conducted in various ways. For example, an inkjet coating liquid containing an oxazoline group-containing resin, an alkanediol, a surfactant, and water (for example, patent literature 3), or an inkjet ink containing a hydroxyl group-containing carboxylic acid ester, a surfactant, and water (for example, see Patent Document 4) has been proposed.

Japanese Unexamined Patent Publication No. 2012-155644 Japanese Unexamined Patent Publication No. 2015-200775 Specification of US Patent Application Publication No. 2013/29045 Japanese Unexamined Patent Publication No. 2013-87207

However, the coating liquids and inks disclosed in Patent Literatures 3 and 4 have not been sufficiently studied from the viewpoint of forming a coating film on a glass substrate. When drying, there were problems in appearance, such as occurrence of non-uniformity or non-uniformity of the film thickness.

The present invention has been devised in view of the problems of the prior art, and an object of the present invention is to provide a colored resin composition capable of forming a colored film with good appearance by suppressing stains and unevenness even when applied by spray or inkjet.

As a result of earnestly examining to solve the above-mentioned problems, the inventors of the present invention found that the above-mentioned problems could be solved by combining specific surfactants.

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

A colored resin composition containing at least (A) a coloring agent, (B) a binder resin, (C) an organic solvent, and two or more (D) surfactants, wherein as the surfactants (D1) a polyether-modified siloxane-based surfactant and (D2) A colored resin composition containing a silicone-modified acrylic surfactant, wherein the total content of the surfactants (D1) and (D2) is 200 ppm or more and 1500 ppm or less in the colored resin composition.

According to the present invention, even when applied by spray or inkjet, it is possible to form a colored film with good appearance while suppressing unevenness and unevenness. Moreover, by using the colored resin composition of the present invention, a decorative substrate for a touch panel having a good appearance can be obtained.

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

The colorant resin composition of the present invention contains at least (A) a colorant, (B) a binder resin, (C) an organic solvent, and two or more (D) surfactants, and (D1) a polyether-modified siloxane-based surfactant. It contains a surfactant and (D2) a silicone-modified acrylic surfactant, and the total content of the surfactants (D1) and (D2) is 200 ppm or more and 1500 ppm or less in the colored resin composition. (A) The coloring material has an action of coloring the resin composition, and (B) the binder resin has an action of retaining each component of the colored resin composition. (C) The organic solvent has an action of uniformly dissolving or dispersing the (A) coloring material in the colored resin composition, while forming a colored film from the colored resin composition, unevenness tends to occur easily due to volatilization during drying of the coating film. . Therefore, in the present invention, by containing a specific amount of the specific surfactant, even when the colored resin composition is applied on a substrate by spray or inkjet, poor coating properties such as stains and unevenness such as Bernard cell during drying of the coating film are suppressed, It becomes possible to form a colored film with a good appearance.

(D1) The polyether-modified siloxane-based surfactant has an action of reducing the interfacial tension of the colored resin composition on the substrate. For this reason, (D1) by containing a polyether-modified siloxane-based surfactant, even when the colored resin composition is applied onto a substrate by spraying or inkjetting, the drawn droplet spreads wet on the substrate, and the paintability such as staining is improved. defects can be suppressed. However, in the organic solvent-based colored resin composition, since the effect of reducing the surface tension of the polyether-modified siloxane-based surfactant is low, there is a problem that non-uniformity such as Bernard cells easily occurs during drying of the coating film. On the other hand, silicone-based surfactants and fluorine-based surfactants have an action 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 applied onto the substrate by spray or inkjet, there is a problem that stains tend to occur. Therefore, as a result of intensive examination of a surfactant capable of suppressing both the coating defect when the colored resin composition is applied on a substrate by spray or inkjet and the drying defect during coating film drying, (D1) polyether modification It was found that the subject could be solved by combining a siloxane-based surfactant and (D2) a silicone-modified acrylic-based surfactant. That is, (D1) containment of a polyether-modified siloxane-based surfactant suppresses applicability defects such as stains, and (D2) containment of a silicone-modified acrylic-based surfactant suppresses an increase in contact angle on a substrate while increasing surface tension. It was found that the non-uniformity at the time of coating film drying can be suppressed by reducing.

(D1) Examples of polyether-modified siloxane-based surfactants include 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 of 2 to 18, m represents an integer of -1 to 50, and n represents an integer of 1 to 8. Here, in the case of m = -1, general formula (1) is represented by the following general formula (2).

It is preferable that the polyether chain is long from the viewpoint of further reducing the interfacial tension of the colored resin composition on the glass substrate. For this reason, a is preferably 5 or more, and more preferably 10 or more. Moreover, as for a, from a viewpoint of compatibility with other resin, 18 or less are preferable. Moreover, m is preferably 1 or more from the viewpoint of further reducing the surface tension of the colored resin composition. 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 still more preferably 3 or less.

(D1) A commercially available surfactant may be used as the polyether-modified siloxane surfactant, and examples of the compound having a structure represented by the general formula (1) include "BYK" (registered trademark)-345 and "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 Co., Ltd.), etc. are mentioned. You may contain 2 or more types of these. Among these, "BYK"-347, "BYK"-348, "BYK"-349, etc., in which a in the above general formula (1) is 5 or more are preferable.

(D2) Examples of silicone-modified acrylic surfactants include compounds having a structure represented by the following general formula (3).

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

(D2) A commercially available surfactant may be used as the silicone-modified acrylic surfactant, and as a compound having a structure represented by the above general formula (2), for example, "BYK"-3550 and "BYK"-SILXLEAN3700 (both manufactured by BYK Chemie) production), etc. You may contain 2 or more types of these.

The total content of (D1) polyether-modified siloxane-based surfactant and (D2) silicone-modified acrylic surfactant in the colored resin composition of the present invention is 200 ppm or more and 1500 ppm or less in the colored resin composition. If the total content of these is less than 200 ppm, the interfacial tension of the colored resin composition increases and the contact angle increases, so that coating defects such as stains tend to occur, and since the surface tension of the colored resin composition increases, Bernard cell etc. unevenness is likely to occur. 300 ppm or more is preferable and, as for these total content, 400 ppm or more is more preferable. On the other hand, when the total content of these exceeds 1500 ppm, the surface tension of the coating solution is excessively lowered, so dry unevenness occurs. In addition, the surfactant bleeds out on the surface of the coating film, and the applicability or adhesion on the colored resin film is lowered. As for these total content, 800 ppm or less is preferable.

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

The content of the (D2) silicone-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, and in order to make the surface tension within the above range, the surface tension can be easily adjusted to the preferred range described later. can be adjusted

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

(A) As a coloring material, an organic pigment, an inorganic pigment, dye etc. are mentioned, for example. You may contain 2 or more types of these.

Examples of organic pigments include diketopyrrolopyrrole pigments; azo 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, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, and violanthrone; quinacridone-based pigments; dioxazine-based pigments; perinone pigments; perylene-based pigments; thioindigo-based pigments; isoindoline-based pigments; isoindolinone-based pigments; quinophthalone pigments; threnic pigment; metal complex pigments; and the like.

Examples of inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, bengala, molybdenum red, molybdenum orange, Chrome Vermillion, Yellow Lead, Cadmium Yellow, Yellow Iron Oxide, Titanium Yellow, Chromium Oxide, Viridian, Titanium Cobalt Green, Cobalt Green, Cobalt Chrome Green, Victoria Green, Ultramarine Blue, Prussian Blue, Cobalt Blue, Cerulean Blue, Cobalt Silica Blue, Cobalt zinc silica blue, manganese violet, cobalt violet, etc. are mentioned.

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

Specific examples of typical pigments and dyes are as follows when indicated by color index (CI) numbers.

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 and the like.

Examples of the orange pigment 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 and the like.

Moreover, as an example of a purple pigment, Pigment Violet (hereinafter abbreviated as PV) 19, PV23, PV29, PV30, PV32, PV37, PV40, PV50 etc. are mentioned.

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. are used.

Moreover, as an example of a green pigment, Pigment Green (hereinafter abbreviated as PG) 7, PG10, PG36, PG58 etc. are mentioned.

Examples of the black pigment include black organic pigments, mixed color organic pigments, and inorganic pigments. As a black organic pigment, carbon black, perylene black, aniline black etc. are mentioned, for example. Examples of mixed color organic pigments include those obtained by combining two or more kinds of red, blue, green, purple, yellow, magenta, and cyan pigments to simulate blackness. Examples of inorganic pigments include fine particles of metals such as graphite, titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, oxides, composite oxides, sulfides, nitrides, and oxynitrides of these metals. can be heard Among these, carbon black and titanium nitride are preferable because they have high light-shielding properties. Examples of the white pigment include titanium dioxide, barium carbonate, zirconium oxide, calcium carbonate, barium sulfate, alumina white, and silicon dioxide.

Examples of dyes include, for example, C.I. 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 C.I. 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, C.I. Reactive Red 3，13，17，19，21，22，23，24，29，35，37，40，41，43，45，49，55 C.I. Basic Red 12，13，14，15，18，22，23，24，25，27，29，35，36，38，39，45，46, C.I. Direct Violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101, C.I. Acid Violet 5, 9, 11, 34, 43, 47, 48, 51, 75, 90, 103, 126, C.I. Reactive Violet 1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34, C.I. Basic Violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48, C.I. 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, C.I. 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, C.I. Reactive Yellow 2，3，13，14，15，17，18，23，24，25，26，27，29，35，37，41，42 C.I. Basic Yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40, C.I. Acid Green 16, C.I. Acid Blue 9，45，80，83，90，185, C.I. Basic Orange 21, 23 etc. are mentioned.

As binder resin (B), an epoxy resin, an acrylic resin, a siloxane resin, a polyimide resin etc. are mentioned, for example. You may contain 2 or more types of these. Among these, an acrylic resin and a polyimide resin are preferable, and can improve the heat resistance of a coating film, the storage stability of a colored resin composition, etc. Further, in forming a pattern such as a black matrix, an alkali-soluble resin is preferably used from the viewpoint of more easily forming a pattern.

The alkali-soluble resin in the present invention refers to a resin having one or more alkali-soluble groups. As an alkali-soluble group, a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a thiol group etc. are mentioned, for example. As alkali-soluble resin, what has a carboxyl group is preferable, and the copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound, and the acrylic resin which has an ethylenically unsaturated group in a side chain are more preferable.

Examples of unsaturated carboxylic acids include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid, acid anhydrides thereof, and phthalic mono(2-( polyhydric carboxylic acid monoesters such as meth)acryloyloxyethyl); and the like. You may use 2 or more types of these. Among these, acrylic acid and methacrylic acid are preferable from the viewpoint of sensitivity at the time of exposure and development.

Examples of the ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, and n-butyl acrylate. , n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, meta unsaturated carboxylic acid alkyl esters such as n-pentyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, and benzyl methacrylate; Aromatic vinyl compounds, such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, and (alpha)-methylstyrene; (crosslinked) cyclic hydrocarbon compounds such as tricyclodecanyl (meth)acrylate; unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; aliphatic conjugated dienes such as 1,3-butadiene and isoprene; Polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, etc. which have an acryloyl group or methacryloyl group at the terminal are mentioned. You may use 2 or more types of these. Among these, benzyl acrylate and benzyl methacrylate are preferable from the viewpoint of dispersion stability and pattern processability.

Examples of the acrylic resin having an ethylenically unsaturated group in the side chain include copolymers described in Japanese Patent No. 3120476 and Japanese Unexamined Patent Publication No. 8-262221, and commercially available acrylic resins such as photocurable resin ""CYCLOMER" ( registered trademark) P” (Daicel Corporation), alkali-soluble cardo resin, and the like.

5,000 or more are preferable and, as for the weight average molecular weight (Mw) of alkali-soluble resin, 8,000 or more are more preferable from a viewpoint of improving photosensitivity. On the other hand, the Mw of the alkali-soluble resin is preferably 40,000 or less from the viewpoint of improving solubility in ester solvents and alkaline 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 standard polystyrene calibration curve.

As for the acid value of alkali-soluble resin, 60-150 (mgKOH/g) is preferable.

In the colored resin composition of the present invention, the content ratio (A)/(B) (mass ratio) of (A) the coloring material and (B) the binder resin is 20/80 or more from the viewpoint of the coloring strength of the colored film obtained from the colored resin composition. It is preferable, and 40/60 or more is more preferable. On the other hand, the content ratio (A)/(B) (mass ratio) of the coloring material (A) and the binder resin (B) is preferably 90/10 or less from the viewpoint of the dispersion stability of the coloring material (A).

(C) Examples of organic solvents include aliphatic hydrocarbons, carboxylic acid esters, ketones, ethers, and alcohols. You may contain 2 or more types of these. Among these, carboxylic acid esters, ketones, and ethers are preferable.

Examples of carboxylic acid esters include benzyl acetate, ethyl benzoate, γ-butyrolactone, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, 3-methoxy-3- Methyl-butyl acetate, diethyl oxalate, ethyl acetoacetate, cyclohexyl acetate, 3-methoxy-butyl acetate, methyl acetoacetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isopentylpropionate , propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, pentyl acetate, and propylene glycol monomethyl ether acetate.

As a ketone, cyclopentanone, cyclohexanone, etc. are mentioned, for example.

Examples of the ether include 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.

Examples of alcohols include 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, and 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, 3-methoxy-butyl acetate and propylene glycol monomethyl ether are preferred. acetic acid esters such as acetate; Propionic acid esters such as propylene glycol monomethyl ether propionate are more preferable.

Examples of organic solvents other than those described above include aliphatic esters such as ethyl acetate, butyl acetate, and isopentyl acetate, xylene, ethylbenzene, and solvent naphtha.

When the colored resin composition of the present invention is applied to a curved substrate by spray or inkjet, it is preferable to contain two or more organic solvents (C) in order to appropriately adjust the volatility and drying characteristics. Specifically, it is preferable to contain an organic solvent having a boiling point of 150°C or more and 230°C or less under atmospheric pressure and an organic solvent having a boiling point of less than 150°C under atmospheric pressure. From the viewpoint of suppressing the aggregation of (A) the colorant caused by drying of the coating liquid in the nozzle, (C) an organic solvent having a boiling point of 150 ° C. or more and 230 ° C. or less under atmospheric pressure with respect to 100 parts by mass of the organic solvent in total. It is preferable to contain 10 mass parts or more. 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, (C) an organic solvent having a boiling point of 150 ° C. or more and 230 ° C. or less under atmospheric pressure with respect to a total of 100 parts by mass of the organic solvent It is preferable to contain 75 parts by mass or less. As for the boiling point of the organic solvent whose boiling point under atmospheric pressure is 150 degreeC or more and 230 degreeC or less, 150 degreeC or more and 200 degreeC or less are more preferable.

The colored resin composition of the present invention preferably has photosensitivity from the viewpoint of more easily forming a pattern in forming a pattern such as a black matrix, and preferably contains a reactive monomer and a photo-radical polymerization initiator.

As a reactive monomer, a monofunctional or polyfunctional acryl monomer, an acryl oligomer, etc. are mentioned. You may contain 2 or more types of these. Among these, a polyfunctional acrylic monomer is preferable.

Examples of the polyfunctional acrylic monomer include bisphenol A diglycidyl ether (meth)acrylate, poly(meth)acrylate carbamate, modified bisphenol A epoxy (meth)acrylate, and 1,6-hexanediol adipic acid. (meth)acrylic acid ester, phthalic anhydride propylene oxide (meth)acrylic acid ester, diethylene glycol trimellitic acid (meth)acrylic acid ester, rosin-modified epoxy di(meth)acrylate, alkyd-modified (meth)acrylate, tripropylene glycol di (meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate Rate, triacryl formal, pentaerythritol tetra(meth)acrylate or its acid modification, dipentaerythritol hexa(meth)acrylate or its acid modification, dipentaerythritol penta(meth)acrylate or its acid modification , 2,2-bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]propane, bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]methane, bis[4 -(3-acryloxy-2-hydroxypropoxy)phenyl]sulfone, bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]ether, 4,4'-bis[4-(3 -Acrylicoxy-2-hydroxypropoxy)phenyl]cyclohexane, 9,9-bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3- Methyl-4-(3-acryloxy-2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3-chloro-4-(3-acryloxy-2-hydroxypropoxy)phenyl]flu orene, bisphenoxyethanol fluorene diacrylate, bisphenoxyethanol fluorene dimethacrylate, biscresol fluorene diacrylate, biscresol fluorene dimethacrylate and the like. Examples of the polyfunctional acrylic oligomer include fluorene diacrylate oligomers described in Japanese Patent No. 3621533 and Japanese Unexamined Patent Publication No. 8-278630.

The sensitivity and processability of the colored resin composition can be adjusted by selecting and combining these polyfunctional monomers and oligomers. In particular, in order to improve the sensitivity, a polyfunctional acrylic monomer having 3 or more functional groups, more preferably 5 or more, is preferable, and dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate or an acid modification thereof are preferred. Sieve is preferred. From the viewpoint of developability and processability, an alkali-soluble monomer containing an unsaturated group obtained by reacting a polybasic acid carboxylic acid or an acid anhydride thereof with a reaction product of an epoxy compound having two glycidyl ether groups and methacrylic acid is preferably used. Further, from the viewpoint of the pattern shape during development, a (meth)acrylate having a highly water-repellent fluorene ring containing many aromatic rings in the molecule is preferable.

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

As an optical radical polymerization initiator, an alkylphenone system optical radical polymerization initiator, an oxime ester system optical radical polymerization initiator, etc. are mentioned, for example. You may contain 2 or more types of these.

Examples of the alkylphenone-based photo-radical polymerization initiator include α-aminoalkylphenone-based photo-radical polymerization initiators, α-hydroxyalkyl phenone-based photo-radical polymerization initiators, benzophenone-based photo-radical polymerization initiators, and thiochic acid. Tone-based photo-radical polymerization initiator, imidazole-based photo-radical polymerization initiator, benzothiazole-based photo-radical polymerization initiator, benzoxazole-based photo-radical polymerization initiator, carbazole-based photo-radical polymerization initiator, triazine-based photo-radical polymerization initiator , inorganic radical optical polymerization initiators such as phosphorus-based radical optical polymerization initiators and titanate; and the like. Among these, an α-aminoalkylphenone-based optical radical polymerization initiator is preferable from the viewpoint of improving the sensitivity. Examples of the alkylphenone-based photo-radical polymerization initiator include 2,2-diethoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, manufactured by BASF. "IRGACURE" (registered trademark) 369 of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, manufactured by BASF "IRGACURE" 379 of 2-(dimethylamino)-2-[ (4-methylphenyl)methyl]-1-[4-(4-morphonyl)phenyl]-1-butanone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane -1-one etc. are mentioned.

Examples of the oxime ester photo-radical polymerization initiator include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], which is "IRGACURE" OXE01 manufactured by BASF, for example, manufactured by BASF. "IRGACURE" Ethanone, OXE02, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime), manufactured by ADEKA CORPORATION "ADEKA" (registered trademark) OPTOMER N-1818, N-1919, ADEKA ARKLS NCI-831 and the like.

Benzophenone-based photo-radical polymerization initiator, thioxanthone-based photo-radical polymerization initiator, imidazole-based photo-radical polymerization initiator, benzothiazole-based photo-radical polymerization initiator, benzoxazole-based photo-radical polymerization initiator, carbazole-based photo-radical polymerization initiator Examples of the radical polymerization initiator, triazine-based photo-radical polymerization initiator, phosphorus-based photo-radical polymerization initiator, inorganic photo-radical polymerization initiator such as titanate, etc. include benzophenone, N,N'-tetraethyl-4,4' -Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2 -Chlorothioxanthone, t-butyl anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer , 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4-(p-methoxyphenyl)-2,6-di-(trichloromethyl)-s-triazine, and the like.

The content of the radical photopolymerization initiator in the colored resin composition of the present invention is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total content of (B) the binder resin and the reactive monomer.

The colored resin composition of the present invention preferably contains a polymer dispersing agent, and (A) the coloring material can be uniformly and stably dispersed in the colored resin composition. Examples of the polymer dispersant include polyester polymer dispersants, acrylic polymer dispersants, polyurethane polymer dispersants, polyallylamine polymer dispersants, carbodiimide polymer dispersants, and the like. You may contain 2 or more types of these. The polymeric dispersant can be appropriately selected depending on the type of (A) coloring material.

Among the polymer dispersants, there are various dispersants such as dispersants having only an amine value, dispersants having only an acid value, dispersants having both an amine value and an acid value, and dispersants having neither an amine value nor an acid value. It is preferable to use, and a polymer dispersant having only an amine value is preferable. 10 or more and 100 or less are preferable, and, as for the amine value of this polymer dispersing agent, 10 or more and 60 or less are more preferable.

Specific examples of the dispersant having only an amine value 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 LP N6919 , DISPERBYK LP N21116, DISPERBYK LP N21234, DISPERBYK 9075, DISPERBYK 9077 (above, manufactured by BYK Chemie); EFKA 4015, 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 4 402, EFKA 4403, EFKA 4800 (and above, manufactured by BASF); ASISPER-PB711 (manufactured by Ajinomoto Fine-Techno Co., Inc.); and the like.

Among dispersants having only an amine value, those having at least a tertiary amino group are more preferable, and specific examples include DISPERBYK LP N6919 and DISPERBYK LP N21116.

Specific examples of the polymer dispersant having an amine value and an acid value include DISPERBYK 142, DISPERBYK 145, DISPERBYK 2001, DISPERBYK 2010, DISPERBYK 2020, DISPERBYK 2025, DISPERBYK 9076, Anti-Terra-205 (above, manufactured by BYK Chemie); SOLSPERSE 24000 (manufactured by The Lubrizol Corporation); ASISPER-PB821, ASISPER-PB880, ASISPER-PB881 (above, manufactured by Ajinomoto Fine-Techno Co., Inc.), etc. are mentioned.

The content of the polymer dispersant in the colored resin composition of the present invention is preferably 1 part by mass or more, and preferably 3 parts by mass or more with respect to 100 parts by mass of the coloring material content (A) from the viewpoint of dispersing the coloring material more stably (A). more preferable than this On the other hand, when the colored resin composition of the present invention has photosensitivity, the content of the polymer dispersant from the viewpoint of photosensitivity is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less with respect to 100 parts by mass of the coloring material content (A). do.

The colored resin composition of the present invention may contain surfactants (D) other than the above (D1) and (D2), and unevenness during drying can be further suppressed to improve the flatness of the colored film. Examples of surfactants (D) other than the above (D1) and (D2) 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 having polydimethylsiloxane or the like as a main skeleton; fluorine-based surfactants; An acrylic surfactant etc. are mentioned.

When it contains (D1) and (D2) other than (D2) surfactant, its content is preferably within the range of not impairing the effects of (D1) and (D2), specifically, 1000 ppm or less in the colored resin composition. It is preferable, and 500 ppm or less is more preferable.

The photosensitive colored resin composition of the present invention preferably contains an adhesion improving agent such as a silane coupling agent, and can improve the adhesion between the coating film and the base substrate. As a silane coupling agent, the silane coupling agent which has functional groups, such as a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, and an amino group, is mentioned. Specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-( 3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxysilane) Toxyethoxy) silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethyne Toxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene ) Preferred are propylamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, and p-styryltrimethoxysilane.

The content of the adhesion improving agent in the colored resin composition of the present invention is from the viewpoint of further improving the adhesiveness in the solid content of the colored resin composition, that is, (A) coloring material, (B) 1 of 100% by mass of the binder resin and additives in total Mass % or more is preferable, and 2 mass % or more is more preferable. On the other hand, when the colored resin composition of the present invention has photosensitivity, the content of the adhesion improving agent from the viewpoint of improving the pattern resolution by alkali development is preferably 15% by mass or less in the solid content of the colored resin composition, and 10% by mass or less is more desirable.

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

The surface tension at 25 ° C. of the colored resin composition of the present invention is preferably 24 mN / m or more, more preferably 25 mN / m or more, from the viewpoint of further suppressing the thinning of the edge in the coating film after drying. 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, more preferably 27.5 mN / m or less, from the viewpoint of suppressing uneven drying more. In addition, surface tension is taken as the value measured at 25 degreeC using the platinum plate by the Wilhelmy method (plate method, vertical plate method). Surface tension at 25 ° C. of the colored resin composition of the present invention, for example, (D2) can be adjusted by the content of the silicone-modified acrylic surfactant, as a method of making the surface tension within the above range, for example, (D2 ) A method of making the content of the silicone-modified acrylic surfactant within the above-described preferred range is exemplified.

The contact angle of the colored resin composition of the present invention on the alkali-free glass 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 applied on a substrate by spray or inkjet, the smaller the contact angle, the easier it is to bind the landed droplets, and the occurrence of uncoated areas can be suppressed. For this reason, the contact angle of the colored resin composition of the present invention on the alkali-free glass is preferably 13° or less, more preferably 12° or less, and more preferably 11° or less. In addition, the contact angle is a value measured by dropping the colored resin composition on an alkali-free glass (#1737, manufactured by Corning Incorporated) washed with an alkali detergent and using a portable contact angle meter. The contact angle of the colored resin composition of the present invention on the alkali-free glass can be adjusted, for example, by the content of (D1) polyether-modified siloxane-based surfactant, as a method of making the contact angle within the above range, for example, (D1) A method of making the content of the polyether-modified siloxane-based surfactant within the above-described preferred range is exemplified.

The viscosity at 25 ° C. of the colored resin composition of the present invention is preferably 2 mPa·s or more from the viewpoint of suppressing the flow of the coating liquid and making the film thickness more uniform even when applying the colored resin composition on a substrate having an inclination. , more preferably 3 mPa·s or more. In addition, the viscosity of the colored resin composition of the present invention at 25°C is such that when the colored resin composition of the present invention is applied on a substrate by spraying or inkjet, it is easy to bind droplets that have landed due to the flow of droplets, and the uncoated area From the viewpoint of suppressing generation, 20 mPa·s or less is preferable, and 15 mPa·s or less is more preferable. In addition, the viscosity is a value at 100 rpm measured with a cone plate type viscometer set at 25.0±0.2°C.

Next, the manufacturing method of the colored resin composition of this invention is demonstrated. A method of dispersing (A) a coloring material in a resin solution containing (B) a binder resin and (C) an organic solvent using a disperser, and adding (D) a surfactant and other components as necessary to the resulting dispersion. Common. From the viewpoint of dispersion stability, it is preferable to blend 5 to 50 parts by mass of the binder resin (B) with respect to 100 parts by mass of the colorant (A), and more preferably 7 to 40 parts by mass.

As a disperser, a ball mill, a sand grinder, a three-roll mill, a high-speed impact mill, etc. are mentioned, for example. A bead mill is preferable from the viewpoints of dispersion efficiency and microdispersion. Examples of the bead mill include coball mill, basket mill, pin mill, and dyno mill.

Examples of beads of the bead mill include titania beads, zirconia beads, and zircon beads. The bead diameter 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 particle diameter of secondary particles formed by aggregation of the primary particles are small, it is preferable to use fine dispersion beads having a bead diameter of 0.03 mm or more and 0.10 mm or less. In this case, it is preferable to disperse using a bead mill having a separator by a centrifugal separation method capable of separating fine dispersed beads from the dispersion. On the other hand, when dispersing the (A) colorant containing coarse particles of the order of submicrons, it is preferable to use dispersion beads of 0.10 mm or more, and (A) the colorant is more finely dispersed by a higher grinding force. can make it

The colored film of the present invention can be obtained by curing the colored resin composition of the present invention. A colored resin composition having negative photosensitivity will be described as an example for a method of forming a colored film from the colored resin composition.

A photosensitive colored resin composition is applied onto a substrate to obtain a coating film. Examples of the substrate include transparent substrates such as soda glass, non-alkali glass, and quartz glass, silicon wafers, ceramic substrates, and gallium arsenide substrates. Examples of the coating method include spin coating using a spinner, spray coating, inkjet coating, die coating, and roll coating, but spray coating and inkjet coating are preferable in the present invention. The film thickness of the coating film can be appropriately selected depending on the application method or the like. It is common to make the film thickness after drying 1-150 micrometers.

The obtained coating film is dried to obtain a dried film. As a drying method, heat drying, air drying, vacuum drying, infrared irradiation etc. are mentioned, for example. As a heat drying apparatus, an oven, a hot plate, etc. are mentioned, for example. The drying temperature is preferably 50 to 150°C, and the drying time is preferably 1 minute to several hours.

The resulting dried film is irradiated with actinic rays through a mask having a desired pattern to obtain an exposed film. Examples of actinic rays to be irradiated include ultraviolet rays, visible rays, electron beams, and X-rays. The colored resin composition of the present invention is preferably irradiated with i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp.

By developing the obtained exposure film using an alkaline developer or the like, an unexposed portion is removed and a pattern is obtained. As an alkaline compound used for an alkaline developing solution, For example, Inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH), quaternary ammonium salts such as choline; alcohol amines such as triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, and diethylaminoethanol; Cyclic pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane, morpholine, etc. Organic alkalis, such as amines, are mentioned.

0.01-50 mass % is common, and, as for the density|concentration of the alkaline compound in alkaline developing solution, 0.02-1 mass % is preferable. In addition, in order to make the pattern shape after image development more favorable, you may add 0.1-5 mass % of surfactants, such as a nonionic surfactant. In the case where the developing solution is an alkaline aqueous solution, a water-soluble organic solvent such as ethanol, γ-butyrolactone, dimethylformamide, or N-methyl-2-pyrrolidone may be added to the developing solution.

As a developing method, a dipping method, a spray method, a paddle method, etc. are mentioned, for example. It does not matter even if you rinse-clean using pure water etc. to the obtained pattern.

A patterned colored film can be obtained by heat-processing (post-baking) the obtained pattern. The heat treatment may be performed in air, in a nitrogen atmosphere, or in a 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 may be changed continuously or may be changed stepwise.

When the colored resin composition of the present invention contains a black (A) coloring material, the colored resin composition is a light-shielding image such as a black matrix of a color filter provided with a liquid crystal display device, etc., a colored barrier rib inside an organic EL display, and a touch panel. It can use suitably for formation of the colored film of the decorative board|substrate provided with this.

It is preferable that the decorative substrate for touch panels of this invention has the above-mentioned colored film, transparent electrode, transparent insulating film, and protective film on a transparent substrate. In addition, formation of each film can be performed by the method described in Unexamined-Japanese-Patent No. 2009-301767, for example.

(Example)

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples, but the present invention is not limited to the following Examples.

<Evaluation method>

「Surface tension」

About the photosensitive black resin composition obtained by each Example and the comparative example, the surface tension was measured at 25 degreeC using the platinum plate using automatic surface tensiometer K11 (made by KRUSS).

"Contact angle"

The photosensitive black resin composition obtained in each Example and Comparative Example was dropped onto alkali-free glass (#1737, manufactured by Corning Incorporated) cleaned with an alkali detergent (HAEMOSOL HEM026-058 (manufactured by WAKENYAKU CO., LTD.)) , The contact angle was measured using a portable contact angle meter PCA-1 (manufactured by Kyowa Interface Science Co., LTD.).

"viscosity"

About the photosensitive black resin composition obtained by each Example and the comparative example, the viscosity in 100 rpm was measured using the viscosity meter (RE105L by TOKI SANGYO CO., LTD.) which set the temperature to 25.0±0.2 degreeC.

"Paper stain"

The prebaked films obtained in each Example and Comparative Example were visually observed under a halogen condensing light having an illuminance of 50,000 nm/m 2 , and the presence or absence of uneven coating was evaluated according to the following criteria. From the point of view of industrial use, A and B were regarded as acceptable.

A: Light leakage is not observed in a state where a light is turned on from under the substrate.

B: There is no uncoated area on the substrate, but light leakage is observed in a state where a light is turned on from under the substrate.

C: There is an uncoated area on the substrate.

"Dry unevenness"

The prebaked films obtained in each Example and Comparative Example were visually observed under a fluorescent lamp and a Na lamp, respectively, and the presence or absence of uneven drying was evaluated according to the following criteria. From the point of view of industrial use, A and B were regarded as acceptable.

A: Non-uniformity was not recognized in the observation of the coating film under fluorescent light and Na lamp.

B: Non-uniformity is not observed in the coating film observation under a fluorescent lamp, but non-uniformity is observed in the coating film observation under a Na lamp.

C: Non-uniformity is observed in coating film observation under fluorescent light.

<Synthesis of acrylic polymer>

[Synthesis Example 1]

After synthesizing a methyl methacrylate/methacrylic acid/styrene copolymer (weight composition ratio 30/40/30) by the method described in Example 1 of Japanese Patent No. 3120476, 40 parts by weight of glycidyl methacrylate Then, by reprecipitation with purified water, filtration, and drying, an acrylic polymer (P-1) powder having an average molecular weight (Mw) of 20,000 and an acid value of 110 (mgKOH/g) was obtained.

<Preparation of photosensitive colored resin composition>

[Example 1]

175 g of high-resistance carbon black TPK1227R (manufactured by Cabot Corporation), 171 g of a 35% by weight solution of propylene glycol monoethyl ether acetate of acrylic polymer (P-1), DISPERBYK LP N-21116 (manufactured by BYK Chemie, propylene glycol as a polymer dispersant) 38 g of monoethyl ether acetate (40% by weight solution) and propylene glycol monoethyl ether acetate (PMA) were added to a 616 g tank, and stirred for 20 minutes with a homomixer (manufactured by PRIMIX Corporation) to obtain a preliminary dispersion. After that, the preliminary dispersion is supplied to an Ultra Apex Mill (manufactured by KOTOBUKI KOGYOU.CO., Ltd.) equipped with a centrifugal separator filled with 75% of 0.05 mmφ zirconia beads (manufactured by DAIKEN CHEMICAL CO., LTD., YTZ Ball) Then, dispersion was performed for 3 hours at a rotational speed of 8 m/s to obtain a black dispersion 1 having a solid content concentration of 25% by weight and a colorant/resin (weight ratio) = 70/30.

301.94 g of this black dispersion 1, 185.17 g of a 35% by weight solution of propylene glycol monoethyl ether acetate of acrylic polymer (P-1), 407.79 g of propylene glycol monoethyl ether acetate, 3-methoxy-3-methylbutanol ( MMB) 40.00 g, "ADEKA" (registered trademark) OPTOMER NCI-831 (made by ADEKA Corporation) 3.91 g, "IRGACURE" (registered trademark) 379 (made by BASF) 6.52 g, dipentaerythritol hexaacrylate ( Nippon Kayaku Co., Ltd. DHPA) 45.67 g, 3-acryloxypropyltrimethoxysilane 3.00 g, polyether modified siloxane surfactant BYK 348 (by BYK Chemie) propylene glycol monoethyl ether acetate 10 A photosensitive black resin composition Bk-1 was prepared by mixing 3.00 g of a solution by weight and 3.00 g of a 10% by weight solution of propylene glycol monoethyl ether acetate of silicone-modified acrylic surfactant BYK 3550 (manufactured by BYK Chemie). As a result of evaluation by the above method, the surface tension of the photosensitive black resin composition Bk-1 was 26.8 mN/m, the contact angle was 9.8°, and the viscosity was 5.6 mPa·s.

The photosensitive black resin composition Bk-1 obtained on an alkali-free glass ("1737" manufactured by Corning Incorporated) substrate was applied using a spray coater (manufactured by Asahi Sunac Corporation, rotary atomizing nozzle) at a spray distance of 50 mm, a spray air pressure of 0.1 MPa, and a discharge amount. After coating under conditions of 10 g/min, nozzle speed of 30 m/min, and re-coating pitch of 10 mm, it was prebaked in a hot air oven at 90°C for 10 minutes. As a result of evaluating this prebaked film by the above method, a film having a good appearance was obtained without uneven coating or uneven drying.

After this, SCREEN Holdings Co., Ltd. It exposed through the gray tone mask using the production exposure machine "XG-5000", and developed using the 0.045 mass % potassium hydroxide aqueous solution. Furthermore, it cured at 230 degreeC for 30 minutes. In this way, a black light shielding film BM-1 having a thickness of 3.0 µm was produced.

[Example 2]

Polyether-modified siloxane-based surfactant BYK 348 (manufactured by BYK Chemie) propylene glycol monoethyl ether acetate was added in an amount of 4.00 g of a 10% by weight solution of propylene glycol monoethyl ether acetate and silicone-modified acrylic surfactant BYK 3550 (manufactured by BYK Chemie). Photosensitive black resin composition Bk-2 was prepared in the same manner as in Example 1 except that the amount of the 10% by weight solution of ether acetate was 2.00 g. The surface tension of the photosensitive black resin composition Bk-2 was 27.2 mN/m, the contact angle was 9.2°, and the viscosity was 5.6 mPa·s.

Using the photosensitive black resin composition Bk-2, it carried out similarly to Example 1, and the prebaked film was produced and the evaluation result is shown in Table 1.

[Example 3]

Polyether-modified siloxane-based surfactant BYK 348 (manufactured by BYK Chemie) was added in an amount of 1.50 g of a 10% by weight solution of propylene glycol monoethyl ether acetate and propylene glycol monoethyl of silicone-modified acrylic surfactant BYK 3550 (manufactured by BYK Chemie) A photosensitive black resin composition Bk-3 was prepared in the same manner as in Example 1 except that the amount of the 10% by weight solution of ether acetate was 1.50 g. The surface tension of the photosensitive black resin composition Bk-3 was 27.6 mN/m, the contact angle was 11.7°, and the viscosity was 5.6 mPa·s.

Using photosensitive black resin composition Bk-3, it carried out similarly to Example 1, the prebaking film was produced, and the result of evaluation is shown in Table 1.

[Example 4]

Polyether-modified siloxane-based surfactant BYK 348 (manufactured by BYK Chemie) was added in an amount of 6.00 g of a 10% by weight solution of propylene glycol monoethyl ether acetate and propylene glycol monoethyl of silicone-modified acrylic surfactant BYK 3550 (manufactured by BYK Chemie). A photosensitive black resin composition Bk-4 was prepared in the same manner as in Example 1 except that the amount of the 10% by weight solution of ether acetate was 6.00 g. The surface tension of the photosensitive black resin composition Bk-4 was 24.8 mN/m, the contact angle was 8.2°, and the viscosity was 5.6 mPa·s.

Using the photosensitive black resin composition Bk-4, it carried out similarly to Example 1, and produced the prebaking film|membrane, and the evaluation result is shown in Table 1.

[Example 5]

Polyether-modified siloxane-based surfactant BYK 348 (manufactured by BYK Chemie) propylene glycol monoethyl ether acetate was added in an amount of 4.00 g of a 10% by weight solution of propylene glycol monoethyl ether acetate and silicone-modified acrylic surfactant BYK 3550 (manufactured by BYK Chemie). The same procedure as in Example 1 was performed except that the addition amount of the 10% by weight solution of ether acetate was 2.00 g and 1.00 g of a 10% by weight solution of propylene glycol monoethyl ether acetate of the silicone surfactant BYK 333 (manufactured by BYK Chemie) was added. A photosensitive black resin composition Bk-5 was prepared. The surface tension of the photosensitive black resin composition Bk-5 was 26.8 mN/m, the contact angle was 11.5°, and the viscosity was 5.6 mPa·s.

Using the photosensitive black resin composition Bk-5, it carried out similarly to Example 1, and the prebaked film was produced and the evaluation result is shown in Table 1.

[Example 6]

5.00 g of a 10% by weight solution of propylene glycol monoethyl ether acetate of polyether-modified siloxane surfactant BYK 348 (manufactured by BYK Chemie), and propylene glycol mono of silicone-modified acrylic surfactant BYK 3550 (manufactured by BYK Chemie) A photosensitive black resin composition Bk-6 was prepared in the same manner as in Example 1 except that the amount of the ethyl ether acetate 10% by weight solution added was 1.00 g. The surface tension of the photosensitive black resin composition Bk-6 was 27.8 mN/m, the contact angle was 8.6°, and the viscosity was 5.6 mPa·s.

Using the photosensitive black resin composition Bk-6, it carried out similarly to Example 1, and produced the prebaked film|membrane, The result of evaluation is shown in Table 1.

[Example 7]

1.00 g of a 10% by weight solution of propylene glycol monoethyl ether acetate of polyether-modified siloxane surfactant BYK 348 (manufactured by BYK Chemie), and propylene glycol mono of silicone-modified acrylic surfactant BYK 3550 (manufactured by BYK Chemie) A photosensitive black resin composition Bk-7 was prepared in the same manner as in Example 1 except that the amount of the ethyl ether acetate 10% by weight solution added was 5.00 g. The surface tension of the photosensitive black resin composition Bk-7 was 25.7 mN/m, the contact angle was 12.1°, and the viscosity was 5.6 mPa·s.

Table 1 shows the results of producing and evaluating prebaked films in the same manner as in Example 1 using the photosensitive black resin composition Bk-7.

[Example 8]

A photosensitive black resin composition Bk-8 was prepared in the same manner as in Example 2 except that a 10% by weight solution of propylene glycol monoethyl ether acetate of BYK 347 (manufactured by BYK Chemie) was used as a polyether-modified siloxane surfactant instead of BYK 348. did. The surface tension of the photosensitive black resin composition Bk-8 was 27.0 mN/m, the contact angle was 10.2°, and the viscosity was 5.6 mPa·s.

Using the photosensitive black resin composition Bk-8, it carried out similarly to Example 1, and produced the pre-bake film|membrane, The result of evaluation is shown in Table 1.

[Example 9]

A photosensitive black resin composition Bk-9 was prepared in the same manner as in Example 2, except that a 10% by weight solution of BYK349 (manufactured by BYK Chemie) in propylene glycol monoethyl ether acetate was used as the polyether-modified siloxane-based surfactant instead of BYK 348. . The surface tension of the photosensitive black resin composition Bk-9 was 27.4 mN/m, the contact angle was 9.6°, and the viscosity was 5.6 mPa·s.

Using the photosensitive black resin composition Bk-9, it carried out similarly to Example 1, and produced the prebaked film|membrane, The result of evaluation is shown in Table 1.

[Example 10]

Photosensitive black resin composition Bk in the same manner as in Example 2 except that a 10% by weight solution of propylene glycol monoethyl ether acetate of SILFACE SAG503A (manufactured by Nissin Chemical Co., Ltd.) was used instead of BYK 348 as a polyether-modified siloxane-based surfactant. -10 was prepared. The surface tension of the photosensitive black resin composition Bk-10 was 27.0 mN/m, the contact angle was 8.8°, and the viscosity was 5.6 mPa·s.

Using the photosensitive black resin composition Bk-10, it carried out similarly to Example 1, and produced the prebaking film|membrane, The result of evaluation is shown in Table 1.

[Comparative Example 1]

Propylene glycol monoethyl ether acetate of silicone surfactant BYK 333 (manufactured by BYK Chemie) instead of polyether-modified siloxane-based surfactant BYK 348 (manufactured by BYK Chemie) and silicone-modified acrylic surfactant BYK 3550 (manufactured by BYK Chemie) 10 A photosensitive black resin composition Bk-11 was prepared in the same manner as in Example 1 except that 3.00 g of the weight% solution was added. The surface tension of the photosensitive black resin composition Bk-11 was 26.0 mN/m, the contact angle was 14.2°, and the viscosity was 5.6 mPa·s.

Using the photosensitive black resin composition Bk-11, it carried out similarly to Example 1, and the prebaking film was produced and the evaluation result is shown in Table 1.

[Comparative Example 2]

Polyether-modified siloxane-based surfactant BYK 348 (manufactured by BYK Chemie) and silicone-modified acrylic surfactant BYK 3550 (manufactured by BYK Chemie) fluorine-based surfactant F-477 (manufactured by DIC Corporation) propylene glycol monoethyl ether acetate 10 A photosensitive black resin composition Bk-12 was prepared in the same manner as in Example 1 except that 3.00 g of the weight% solution was added. The surface tension of the photosensitive black resin composition Bk-12 was 26.4 mN/m, the contact angle was 13.7°, and the viscosity was 5.6 mPa·s.

Using the photosensitive black resin composition Bk-12, it carried out similarly to Example 1, and produced the prebaked film|membrane, The result of evaluation is shown in Table 1.

[Comparative Example 3]

A polyether-modified siloxane-based surfactant BYK 348 (manufactured by BYK Chemie) was added in an amount of 3.00 g of a 10% by weight solution of propylene glycol monoethyl ether acetate, and the silicone-modified acrylic surfactant BYK 3550 (manufactured by BYK Chemie) was not added. Other than that, it carried out similarly to Example 1, and prepared the photosensitive black resin composition Bk-13. The surface tension of the photosensitive black resin composition Bk-13 was 28.4 mN/m, the contact angle was 8.8°, and the viscosity was 5.6 mPa·s.

Using the photosensitive black resin composition Bk-13, it carried out similarly to Example 1, and the prebaking film was produced and the evaluation result is shown in Table 1.

[Comparative Example 4]

Polyether-modified siloxane-based surfactant BYK 348 (manufactured by BYK Chemie) was not added, and the addition amount of a 10% by weight solution of propylene glycol monoethyl ether acetate of silicone-modified acrylic surfactant BYK 3550 (manufactured by BYK Chemie) was 3.00 g. Photosensitive black resin composition Bk-14 was prepared in the same manner as in Example 1 except for the above. The surface tension of the photosensitive black resin composition Bk-14 was 26.8 mN/m, the contact angle was 13.2°, and the viscosity was 5.6 mPa·s.

Using the photosensitive black resin composition Bk-14, it carried out similarly to Example 1, and produced the prebaking film|membrane, The result of evaluation is shown in Table 1.

[Comparative Example 5]

0.50 g of a 10% by weight solution of propylene glycol monoethyl ether acetate of polyether-modified siloxane surfactant BYK 348 (manufactured by BYK Chemie), and propylene glycol mono of silicone-modified acrylic surfactant BYK 3550 (manufactured by BYK Chemie) A photosensitive black resin composition Bk-15 was prepared in the same manner as in Example 1 except that the amount of the 10% by weight ethyl ether acetate solution was changed to 1.00 g. In addition, the surface tension of the photosensitive black resin composition Bk-15 was 28.2 mN/m, the contact angle was 13.1°, and the viscosity was 5.6 mPa·s.

Using the photosensitive black resin composition Bk-15, it carried out similarly to Example 1, and the prebaked film was produced and the evaluation result is shown in Table 1.

[Comparative Example 6]

The addition amount of a 10% by weight solution of propylene glycol monoethyl ether acetate of polyether-modified siloxane surfactant BYK 348 (manufactured by BYK Chemie) was 6.00 g, and propylene glycol mono of silicone-modified acrylic surfactant BYK 3550 (manufactured by BYK Chemie) A photosensitive black resin composition Bk-16 was prepared in the same manner as in Example 1 except that the amount of the ethyl ether acetate 10% by weight solution added was 12.00 g. In addition, the surface tension of the photosensitive black resin composition Bk-16 was 23.7 mN/m, the contact angle was 7.6°, and the viscosity was 5.6 mPa·s.

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

It turns out that the photosensitive black resin composition produced in the Example has a good external appearance with the unevenness and nonuniformity suppressed when a dry film was formed on the glass substrate by spray coating.

Even when the colored resin composition of the present invention is applied onto a substrate by spray or inkjet, it is possible to easily provide a colored film with good appearance while suppressing unevenness and unevenness. Therefore, it is possible to efficiently form a high-performance colored pattern that can be used for color filter substrates and decorative substrates for liquid crystal display devices, decorative substrates for touch panels, colored barrier ribs and decorative film substrates for organic EL displays, and the like.

Claims (9)

A colored resin composition containing at least (A) a coloring agent, (B) a binder resin, (C) an organic solvent, and two or more (D) surfactants, wherein as the surfactants (D1) a polyether-modified siloxane-based surfactant and (D2) A colored resin composition containing a silicone-modified acrylic surfactant, wherein the total content of the surfactants (D1) and (D2) is 200 ppm or more and 1500 ppm or less in the colored resin composition. According to claim 1,
The colored resin composition in which the content ratio (D2)/(D1) of the surfactant (D2) to the content of the surfactant (D1) is 0.25 or more and 4.0 or less. According to claim 1 or 2,
The colored resin composition whose surface tension at 25 degreeC is 24 mN/m or more and 28 mN/m or less. According to claim 1 or 2,
A colored resin composition having a contact angle of 1° or more and 13° or less on an alkali-free glass According to claim 1 or 2,
Colored resin composition having a viscosity of 2 mPa·s or more and 20 mPa·s or less at 25°C According to claim 1 or 2,
A colored resin composition containing at least carbon black and/or titanium nitride as the coloring material (A). According to claim 1 or 2,
A colored resin composition further containing a polyfunctional acrylic monomer and an optical radical polymerization initiator. A colored film comprising the colored resin composition according to claim 1 or 2. The decorative substrate for touch panels which has the colored film of Claim 8.