KR20240044426A - Photosensitive composition, color filter substrate, fingerprint sensor and display device - Google Patents

Abstract

A photosensitive composition is provided that has excellent shape retention for uneven portions of an underlying substrate and shows little change in processing characteristics even when left to stand after application. A photosensitive composition containing an alkali-soluble resin having a tricyclodecanyl skeleton, a radically polymerizable compound, a photopolymerization initiator, a colorant, and an organic solvent, wherein the alkali-soluble resin having a tricyclodecanyl skeleton accounts for 20% by mass of the solid content. Photosensitivity that is not less than 40% by mass and satisfies the ratio T/M of the total mass of the solid content excluding the colorant of the photosensitive composition, Tg, and the number of moles M of the carboxyl group contained in the solid content excluding the colorant of the photosensitive composition, of 1300 to 1600. Composition.

Description

Photosensitive composition, color filter substrate, fingerprint sensor and display device

The present invention relates to photosensitive compositions, color filter substrates, fingerprint sensors, and display devices.

Liquid crystal displays are used for a variety of purposes, including televisions, notebook PCs, portable information terminals, smartphones, and digital cameras, taking advantage of their characteristics such as light weight, thinness, and low power consumption. Liquid crystal display devices require optimal colors of 3 to 6 primary colors depending on the application, and color filter substrates that provide various color performances are used.

When forming a colored pixel, a color filter substrate is generally manufactured by applying a photosensitive composition onto the substrate using a slit coater, drying it, and then performing exposure, development, and baking. As a photosensitive composition for a color filter, various photosensitive compositions are known (for example, see Patent Document 1 and Patent Document 2). After these photosensitive compositions are applied onto a substrate, they are exposed and developed using a photolithography mask to form a pattern into a desired shape.

International Publication No. 2017/164127 International Publication No. 2018/151044

Generally, when exposing a photosensitive composition on a substrate, a pattern of a desired shape can be formed at a desired position by adjusting the positional relationship between the substrate and the photolithography mask. When adjusting the positional relationship between the substrate and the photolithography mask, an alignment mark previously formed on the substrate with a coloring composition or the like is used as a reference.

However, when a photosensitive composition is applied on a substrate containing an alignment mark, the position of the alignment mark cannot be specified even if the alignment mark is observed using a camera from above the substrate because the photosensitive composition described above has low shape retention with respect to the substrate. There was a task to do.

In addition, there is a problem that the processing characteristics change significantly when the photosensitive composition is left for a certain period of time after application, and improvement has been required.

The purpose of the present invention is to provide a photosensitive composition that has excellent shape retention for uneven portions of an underlying substrate and shows little change in processing characteristics even when left to stand after application.

The present invention is a photosensitive composition containing an alkali-soluble resin having a tricyclodecanyl skeleton, a radically polymerizable compound, a photopolymerization initiator, a colorant, and an organic solvent, wherein the proportion of the alkali-soluble resin having a tricyclodecanyl skeleton is the solid content. It is 20% by mass or more and 40% by mass or less, and the ratio T/M of the total mass of the solid content excluding the colorant of the photosensitive composition, Tg, and the number of moles M of carboxyl groups contained in the solid content of the photosensitive composition satisfies 1300 or more and 1600 or less. It is a photosensitive composition.

According to the photosensitive composition of the present invention, it is possible to provide a photosensitive composition that has excellent shape retention for the uneven portion of the base substrate and shows little change in processing characteristics even if left to stand after application.

1 is a cross-sectional view when a film containing a photosensitive composition is formed on a glass substrate with a pattern in the shape maintenance evaluation described in the examples, and is a diagram showing the height H and the inclination width L of the resting portion with respect to the pattern. am.

The photosensitive composition of the present invention is a photosensitive composition containing an alkali-soluble resin having a tricyclodecanyl skeleton, a radically polymerizable compound, a photopolymerization initiator, a colorant, and an organic solvent, wherein the alkali-soluble resin having a tricyclodecanyl skeleton accounts for The ratio is 20% by mass or more and 40% by mass or less of the solid content, and the ratio Tg of the total mass of the solid content excluding the colorant of the photosensitive composition and the number of moles M of carboxyl groups contained in the solid content excluding the colorant of the photosensitive composition is 1300. It is a photosensitive composition that satisfies 1600 or less. The photosensitive composition of the present invention has excellent shape retention for the uneven portions of the base substrate, and can suppress changes in processing characteristics even if left to stand after application. Additionally, since the photosensitive composition of the present invention has excellent shape retention properties, when the photosensitive composition is applied on a substrate containing an alignment mark, the film formed on the alignment mark maintains its swollen shape. Therefore, the position can be specified even if the alignment mark is observed from above the substrate using a camera.

(Alkali-soluble resin with tricyclodecanyl skeleton)

The photosensitive composition of the present invention contains an alkali-soluble resin having a tricyclodecanyl skeleton. By containing an alkali-soluble resin having a tricyclodecanyl skeleton, it is excellent in processability and shape retention for uneven portions of the base substrate, and furthermore, changes in processing characteristics can be suppressed even if left to stand after application.

Examples of alkali-soluble resins having a tricyclodecanyl skeleton include acrylic resins, epoxy resins, polyimide resins, urethane resins, urea resins, polyvinyl alcohol resins, melamine resins, polyamide resins, polyamidoimide resins, and polyesters. Resins, polyolefin resins, etc. can be mentioned. You may contain two or more of these. In terms of stability, acrylic resin is preferably used.

Regarding the acrylic resin, examples of ethylenically unsaturated compounds having a tricyclodecanyl skeleton include tricyclodecanyl (meth)acrylate and tricyclodecane dimethanol di(meth)acrylate, and unsaturated carboxyl Copolymers with acids are preferred.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof. You may use two or more of these.

The weight ratio of the unit having a tricyclodecanyl skeleton contained in the alkali-soluble resin having a tricyclodecanyl skeleton is preferably 2% by mass or more and 30% by mass or less in the alkali-soluble resin having a tricyclodecanyl skeleton. The weight ratio of the unit having a tricyclodecanyl skeleton is preferably 30% by mass or less, more preferably 20% by mass of the alkali-soluble resin having a tricyclodecanyl skeleton, from the viewpoint of shape retention with respect to the uneven portion of the base substrate. It is mass % or less, more preferably 15 mass % or less, and even more preferably 12 mass % or less. In addition, from the viewpoint of film stability after application, the weight ratio of the unit having a tricyclodecanyl skeleton contained in the alkali-soluble resin having a tricyclodecanyl skeleton is 1% by mass of the alkali-soluble resin having a tricyclodecanyl skeleton. More is preferable, more preferably 2 mass% or more, and even more preferably 5 mass% or more. In addition, from the viewpoint of blocking the discharge port of the discharge device, the weight ratio of the unit having a tricyclodecanyl skeleton contained in the alkali-soluble resin is preferably 5% by mass or more, more preferably 9% by mass or more of the alkali-soluble resin. am.

The weight ratio of the unit having a tricyclodecanyl skeleton can be determined by calculating the weight of each structural unit based on the molar ratio of each structural unit to the alkali-soluble resin having a tricyclodecanyl skeleton. In addition, in the photosensitive composition, the weight ratio of the unit having a tricyclodecanyl skeleton contained in the alkali-soluble resin having a tricyclodecanyl skeleton can be calculated by the following method. First, with respect to each component contained in the photosensitive composition of the present invention, each component is isolated and purified by methods such as preparative GPC, preparative HPLC, and column purification, and the structure of the alkali-soluble resin having a tricyclodecanyl skeleton is analyzed. It can be calculated. Regarding the structural analysis of an alkali-soluble resin having a tricyclodecanyl skeleton, it can be specifically identified by ¹ H-NMR, ¹³ C-NMR, two-dimensional NMR such as HMBC or HMQC, and from the structural analysis results, alkali It can be calculated by calculating the weight ratio of the tricyclodecanyl skeleton to the entire soluble resin.

The alkali-soluble resin having a tricyclodecanyl skeleton may be a resin obtained by copolymerizing another ethylenically unsaturated compound.

Examples of ethylenically unsaturated compounds include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and sec- (meth)acrylate. Unsaturated alkyl carboxylic acids such as butyl, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and benzyl (meth)acrylate. Aromatic vinyl compounds such as esters, styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, and α-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, glycidyl acrylate, and glycidyl acrylate. Unsaturated carboxylic acid glycidyl esters such as cidyl methacrylate, carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, cyanide vinyl compounds such as acrylonitrile, methacrylonitrile, and α-chloracrylonitrile, Aliphatic conjugated dienes such as 1,3-butadiene and isoprene, polystyrene with a (meth)acryloyl group at the terminal, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polysilicon, etc. Macro monomers, etc. can be mentioned. You may use two or more of these.

The alkali-soluble resin having a tricyclodecanyl skeleton preferably has an ethylenically unsaturated group in the side chain from the viewpoint of film stability after application. Examples of the ethylenically unsaturated group include vinyl group, allyl group, acrylic group, and methacryl group. Examples of the acrylic resin having an ethylenically unsaturated group in the side chain include "Cyclomer" (registered trademark) P (Daicel Chemical Industries, Ltd.), alkali-soluble Cardo resin, and the like.

The double bond equivalent weight of the alkali-soluble resin having a tricyclodecanyl skeleton is preferably 500 or more, more preferably 800 or more, and still more preferably 1,000 or more from the viewpoint of film stability and processability after application. In addition, the double bond equivalent weight of the alkali-soluble resin having a tricyclodecanyl skeleton is preferably 3,000 or less, more preferably 2,000 or less, from the viewpoint of shape retention, processability and reliability for the uneven portion of the base substrate, and further preferably 2,000 or less. Preferably it is 1,500 or less.

It is preferable that the weight average molecular weight of the alkali-soluble resin having a tricyclodecanyl skeleton is 9,000 or more and 200,000 or less. The weight average molecular weight of the alkali-soluble resin having a tricyclodecanyl skeleton is preferably 3,000 or more, and more preferably 9,000 or more from the viewpoint of the strength of the cured film. Moreover, from the viewpoint of shape maintenance of the uneven portion of the base substrate, 10,000 or more is preferable, 20,000 or more is more preferable, and 30,000 or more is still more preferable. In addition, from the viewpoint of stability of the photosensitive composition, compatibility with other components, and film stability after application, the weight average molecular weight of the alkali-soluble resin having a tricyclodecanyl skeleton is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 100,000 or less. Preferably it is 40,000 or less. In addition, from the viewpoint of blocking the discharge port of the discharge device, the weight average molecular weight of the alkali-soluble resin having a tricyclodecanyl skeleton is preferably 40,000 or less, and more preferably 35,000 or less. The weight average molecular weight of the alkali-soluble resin herein refers to the standard polystyrene conversion value measured by gel permeation chromatography.

The content of the alkali-soluble resin having a tricyclodecanyl skeleton contained in the photosensitive composition of the present invention is 20% by mass or more and 40% by mass or less in solid content. If the content of the alkali-soluble resin having a tricyclodecanyl skeleton is less than 20% by mass of the solid content, the shape retention of the uneven portion of the base substrate deteriorates. The content of the alkali-soluble resin having a tricyclodecanyl skeleton is more preferably 22% by mass or more, and still more preferably 25% by mass or more. Moreover, if the content of the alkali-soluble resin having a tricyclodecanyl skeleton is greater than 40% by mass in the solid content, the film stability after application deteriorates. The content of the alkali-soluble resin having a tricyclodecanyl skeleton is preferably 35% by mass or less, and more preferably 30% by mass or less, based on the solid content. Furthermore, from the viewpoint of blocking the discharge port of the discharge device, the content of the alkali-soluble resin having a tricyclodecanyl skeleton is preferably 35% by mass or less, and more preferably 32% by mass or less, based on the solid content.

(Radically polymerizable compound)

The photosensitive composition of the present invention contains a radically polymerizable compound. The radically polymerizable compound referred to herein refers to a compound that reacts by radical polymerization, and refers to a compound with a weight average molecular weight of 1,000 or less. The radically polymerizable compound is preferably a compound having an unsaturated hydrocarbon group. Examples of the unsaturated hydrocarbon group include (meth)acryloyl group, vinyl group, and maleimide group. You may have two or more of these.

Examples of radically polymerizable compounds include dipentaerythritol penta(meth)acrylate, tetratrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. , ethylene oxide-modified or propylene-oxide-modified products such as penta(meth)acryloyloxydipentaerythritol monosuccinic acid ester and dipentaerythritol hexa(meth)acrylate, styrene derivatives, multifunctional maleimide compounds, poly(meth) ) Acrylate carbamate, adipic acid 1,6-hexanediol (meth)acrylic acid ester, phthalic acid propylene oxide (meth)acrylic acid ester, trimellitate diethylene glycol (meth)acrylic acid ester, rosin modified epoxy di(meth)acrylic acid ) Oligomers such as acrylates and alkyd-modified (meth)acrylates, bifunctional (meth)acrylates such as tripropylene glycol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate, and trimethylol. Propane tri(meth)acrylate, triacrylic formal, bisphenoxyethanol fluorene diacrylate, dicyclopentane dienyl diacrylate, alkyl modified products, alkyl ether modified products, and alkyl ester modified products thereof. You can. You may contain two or more of these. From the viewpoint of film stability after application, it is preferable to use pentaerythritol triacrylate as the radically polymerizable compound.

The content of the radically polymerizable compound in the photosensitive composition of the present invention is preferably 40% by mass or more based on the solid content from the viewpoint of patterning properties. On the other hand, from the viewpoint of suppressing film thickness unevenness during film forming and suppressing pattern deformation due to flow during firing, the content of the radical polymerizable compound is preferably 90% by mass or less, and 70% by mass or less, based on the solid content. is more preferable, and 60% by mass or less is still more preferable.

(Photopolymerization initiator)

The photosensitive composition of the present invention contains a photopolymerization initiator. By containing a photopolymerization initiator, sensitivity during patterning can be improved. Here, the photopolymerization initiator refers to a compound that decomposes and/or reacts with light (including ultraviolet rays or electron beams) and generates radicals. Examples of the photopolymerization initiator include oxime ester-based compounds, benzophenone-based compounds, acetophenone-based compounds, oxanthone-based compounds, anthraquinone-based compounds, imidazole-based compounds, benzothiazole-based compounds, benzoxazole-based compounds, and carbazole-based compounds. , triazine-based compounds, phosphorus-based compounds, and titanocene-based compounds.

More specifically, examples of oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), ethanone, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl-4- tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1,3-dioxolanyl) methoxybenzoyl}-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 1,2-octanedione, 1-[4-( Phenylthio)-2-(O-benzoyloxime)], "Adeka Ackles" (registered trademark) N-1919, NCI-930 (manufactured by ADEKA Co., Ltd.), "IRGACURE" (registered trademark) OXE01, OXE02 ( BASF Co., Ltd.) etc. can be mentioned. Examples of benzophenone-based compounds include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. Acetophenone-based compounds include, for example, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, and 1-hydroxycyclohexyl. Phenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propane, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-buta Non, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-( methylthio)phenyl]-2-morpholinopropan-1-one, "IRGACURE" (registered trademark) 369, 379, 907 (manufactured by BASF Corporation), etc. Examples of anthraquinone-based compounds include t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethyanthraquinone, and 1,4-naph. Toquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, etc. are mentioned. Examples of the imidazole-based compound include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer. Examples of benzothiazole-based compounds include 2-mercaptobenzothiazole. Examples of the benzoxazole-based compound include 2-mercaptobenzoxazole. Examples of the triazine-based compound include 4-(p-methoxyphenyl)-2,6-di-(trichloromethyl)-s-triazine. You may contain two or more of these.

From the viewpoint of sensitivity, patterning properties, and processability, the content of the photopolymerization initiator is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 5% by mass or more, based on the solid content excluding the colorant of the photosensitive composition. . On the other hand, from the viewpoint of sensitivity, patterning properties, processability, and heat resistance, the content of the photopolymerization initiator is preferably 30% by mass or less, more preferably 20% by mass or less, and 15% by mass or less, based on the solid content excluding the colorant of the photosensitive composition. is more preferable.

(color material)

The photosensitive composition of the present invention contains a colorant. Colorants include organic pigments, inorganic pigments, dyes, etc., and two or more types of these may be contained. Among these, organic pigments and dyes are preferable from the viewpoint of further improving transmittance.

As a red colorant, for example, C.I. Pigment Red (hereinafter referred to 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 diketopyrrolopyrrole colorants having a bromine group. From the viewpoint of the brightness characteristics of the pixel, PR254 or PR177, a diketopyrrolopyrrole colorant having a bromine group is preferable, and from the viewpoint of brightness, vividness, and prevention of color mixing, it is preferable to use a diketopyrrolopyrrole colorant having a bromine group.

Examples of yellow colorants include organic pigments, inorganic pigments, dyes, etc., such as C.I. Pigment Yellow (hereinafter referred to as “PY”) 12, PY13, PY17, PY20, PY24, PY83, PY86, PY93, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY139, PY147, PY148, PY150, PY15 3, Examples include PY154, PY166, and PY168 (above, all numbers are color index numbers). You may contain two or more of these. From the viewpoint of color purity, light transmittance, and contrast, PY129, PY139, PY150, and PY185 are preferable, and PY150 and PY185 are more preferable.

Examples of green colorants include organic pigments, inorganic pigments, dyes, etc., such as C.I. Pigment green (hereinafter referred to as “PG”) PG1, PG2, PG4, PG7, PG8, PG10, PG13, PG14, PG15, PG17, PG18, PG19, PG26, PG36, PG38, PG39, PG45, PG48, PG50, PG51, Examples include PG54, PG55, PG58, and PG59 (all numbers are color index numbers). You may contain two or more of these.

As an orange colorant, for example, C.I. Pigment Orange (hereinafter referred to as “PO”) 13, PO31, PO36, PO38, PO40, PO42, PO43, PO51, PO55, PO59, PO61, PO64, PO65, PO71, etc. are mentioned.

As a blue colorant, for example, C.I. Pigment Blue (hereinafter referred to as “PB”) 15, PB15:3, PB15:4, PB15:6, PB21, PB22, PB60, PB64, etc. are mentioned.

As a purple colorant, for example, C.I. Pigment Violet (hereinafter referred to as “PV”) 19, PV23, PV29, PV30, PV32, PV37, PV40, PV50, etc. (all numbers above are color index numbers).

Examples of dyes include oil-soluble dyes, acid dyes, direct dyes, basic dyes, and acid mordant dyes. Additionally, the dye may be laked or formed into a salt-forming compound of the dye and a nitrogen-containing compound.

Examples of red, green, blue, purple, or yellow dyes include direct dyes, acid dyes, and basic dyes. Specific examples of these dyes include azo-based dyes, benzoquinone-based dyes, naphthoquinone-based dyes, anthraquinone-based dyes, xanthene-based dyes, cyanine-based dyes, squaryllium-based dyes, croconium-based dyes, and melocyanine-based dyes. Dyes, stilbene-based dyes, diaryl methane-based dyes, trialrylmethane-based dyes, fluorane-based dyes, spiropyran-based dyes, phthalocyanine-based dyes, indigo-based dyes, fulgid-based dyes, nickel complex-based dyes, azulene-based dyes, etc. I can hear it. The dye may be dissolved in the photosensitive composition or dispersed as particles.

In order to increase resistance to heat, light, acid, alkali or organic solvent, etc., the basic dye is preferably a salt-forming compound containing an organic acid such as an organic sulfonic acid or an organic carboxylic acid or a perchloric acid, and a naphthalenesulfonic acid such as tobiasic acid or a perchloric acid. A salt-forming compound containing is more preferable. Likewise, in order to increase resistance to heat, light, acid, alkali or organic solvents, etc., salt-forming compounds containing quaternary ammonium salts, primary to tertiary amines or sulfonamides are preferred as acid dyes and direct dyes.

The content of the colorant is preferably 10% by mass or more, more preferably 20% by mass or more, based on the solid content of the photosensitive composition from the viewpoint of clogging the discharge portion of the applicator. Furthermore, from the viewpoint of film stability, the content of the colorant is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, based on the solid content of the photosensitive composition.

The colorant contained in the photosensitive composition can be identified by laser Raman spectroscopy (Ar + laser (457.9 nm)), mass analysis using a MALDI mass spectrometer, or a time-of-flight secondary ion mass spectrometer.

In addition, the content of the colorant in the photosensitive composition can be quantified by mass analysis using a MALDI mass spectrometer or a time-of-flight secondary ion mass spectrometer, and from the mass of the obtained colorant and the content of other components, the photosensitive composition The proportion (mass %) of the solid content in the solution can be determined. In addition, when the raw material mixing ratio of the photosensitive composition is known, the ratio (mass %) of the solid content in the photosensitive composition can be determined from the mixing amount of the colorant and the mixing amount of other components.

(organic solvent)

The photosensitive composition of the present invention contains an organic solvent. Organic solvents include, for example, diethylene glycol monobutyl ether acetate, benzyl acetate, ethyl benzoate, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, ethylene glycol monobutyl ether acetate, Diethyl oxalate, ethyl acetoacetate, cyclohexyl acetate, 3-methoxy-butylacetate, methyl acetoacetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isopentyl propionate, propylene glycol monomethyl. Ether propionate, pentyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, monoethyl ether, methyl carbitol, ethyl carbitol. Vitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, isopentyl butanol acetate, 3-methyl-2-butanol, 3-methyl -3-methoxybutanol, cyclopentanone, cyclohexanone, xylene, ethylbenzene, solvent naphtha, etc. are mentioned. You may contain two or more of these.

Among the organic solvent components contained in the photosensitive composition of the present invention, it is preferable that the proportion of the organic solvent having a boiling point of 150°C or lower is 80% by mass or more from the viewpoint of shape retention for the uneven portion of the base substrate.

(Other ingredients)

The photosensitive composition of the present invention may further contain a dispersant, chain transfer agent, photosensitizer, polymerization inhibitor, adhesion improver, surfactant, crosslinking agent, etc.

(Dispersant)

The photosensitive composition of the present invention may contain a dispersant such as a pigment derivative along with a colorant. Examples of the dispersant include low-molecular-weight dispersants such as pigment intermediates and derivatives, and high-molecular-weight dispersants. Examples of pigment derivatives include alkylamine modified products of the pigment skeleton, carboxylic acid derivatives, and sulfonic acid derivatives that contribute to appropriate wetting and stabilization of the pigment. Sulfonic acid derivatives of the pigment skeleton are preferred, as they have a significant effect on stabilizing fine pigments.

Examples of polymer dispersants include polyester, polyalkylamine, polyallylamine, polyimine, polyamide, polyurethane, polyacrylate, polyimide, polyamidoimide, and copolymers thereof. You may contain two or more of these. Among these polymer dispersants, it is preferable that the amine value in terms of solid content is 5 to 200 mgKOH/g and the acid value is 1 to 100 mgKOH/g. Among them, a polymer dispersant having a basic group is preferable and can improve the storage stability of the pigment dispersion liquid and the photosensitive composition. Commercially available polymer dispersants having a basic group include, for example, "Solsperse" (registered trademark) (manufactured by Avesia Corporation), "EFKA" (registered trademark) (manufactured by FKA Corporation), and "Azispur" (registered trademark) (Ajinomoto Fine) and "BYK" (registered trademark) (manufactured by Big Chemistry). You may contain two or more of these. Among them, "Solspers" (registered trademark) 24000 (manufactured by Avecia), "EFKA" (registered trademark) 4300, 4330 (manufactured by FKA), 4340 (manufactured by FKA), "Azispur" (registered trademark) PB821, PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd.), "BYK" (registered trademark) 161 to 163, 2000, 2001, 6919, and 21116 (manufactured by Big Chemistry) are preferred.

When the photosensitive composition of the present invention contains a polymer dispersant, the total content of the polymer dispersant and the alkali-soluble resin is preferably 10% by mass or more, and 20% by mass, based on the solid content, from the viewpoint of suppressing film thickness unevenness during film forming. More is more preferable, and 30 mass% or more is still more preferable. On the other hand, from the viewpoint of patterning properties, the total content of the polymer dispersant and the alkali-soluble resin is preferably 60% by mass or less, and more preferably 50% by mass or less, based on the solid content excluding the colorant of the photosensitive composition.

(Chain transfer system)

The photosensitive composition of the present invention may contain a chain transfer agent in addition to the photopolymerization initiator, and the sensitivity can be further improved. Chain transfer agents include, for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, and 2-mer. Captonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2 -Mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl(4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1 -Mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzo Thiazole, mercaptoacetic acid, trimethylolpropane tris(3-mercaptopropionate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4 ,6(1H,3H,5H)-trione), pentaerythritoltetrakis(3-mercaptopropionate), 1,4-bis(3-mercaptobutyryloxy)butane, "Karenz"( Registered trademark) MT PE-1 (manufactured by Showa Denko Co., Ltd.), “Karenz” (registered trademark) MT NR-1 (manufactured by Showa Denko Co., Ltd.), “Kalenz” (registered trademark) MT BD- Mercapto compounds such as 1 (manufactured by Showa Denko Co., Ltd.), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodo and alkyl iodide compounds such as dopropanesulfonic acid. You may contain two or more of these.

(Light sensitizer)

The photosensitive composition of the present invention may further contain a photosensitizer, and examples of the photosensitizer include thioxanthone-based sensitizers, aromatic or aliphatic tertiary amines, and the like. As a thioxanthone-based sensitizer, for example, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthene-9-one, "KAYACURE" (registered trademark) DETX-S (Nippon Kayaku) (Co., Ltd.), etc. can be mentioned. You may contain two or more of these.

(polymerization inhibitor)

The photosensitive composition of the present invention may further contain a polymerization inhibitor, and stability can be improved. Polymerization inhibitors generally have the effect of inhibiting or stopping polymerization by radicals generated by heat, light, radical initiators, etc., and are generally used to prevent gelation of thermosetting resins or to stop polymerization during polymer production. Examples of polymerization inhibitors include hydroquinone, tert-butylhydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, 2,5-bis(1,1-dimethylbutyl)hydroquinone, Catechol, tert-butylcatechol, etc. can be mentioned. You may contain two or more of these. From the viewpoint of the balance between stability and photosensitive properties, the content of the polymerization inhibitor is preferably 0.0001% by mass or more, and more preferably 0.005% by mass or more, based on the solid content. Furthermore, from the viewpoint of the balance between stability and photosensitive properties, the content of the polymerization inhibitor is preferably 1% by mass or less, and more preferably 0.5% by mass or less, based on the solid content.

(Adhesion improving agent)

The photosensitive composition of the present invention may further contain an adhesion improving agent, and the adhesion of the photosensitive composition to the coated film substrate can be improved. Examples of adhesion improvers include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N -(2-Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Silane coupling agents such as methoxysilane can be mentioned. You may contain two or more of these.

(Surfactants)

The photosensitive composition of the present invention may further contain a surfactant, and the applicability of the photosensitive composition and the uniformity of the coating film surface can be improved. Examples of surfactants include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether triethanolamine sulfate, cationic surfactants such as stearylamine acetate and lauryl trimethyl ammonium chloride, lauryl dimethylamine oxide, Amphoteric surfactants such as urylcarboxymethylhydroxyethylimidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate, fluorine-based surfactants and silicone-based surfactants. etc. can be mentioned. You may contain two or more of these. The content of the surfactant is preferably 0.001 to 10% by mass in the photosensitive composition from the viewpoint of in-plane uniformity of the coating film.

(Photosensitive composition)

In the photosensitive composition of the present invention, the ratio T/M of the total mass T (grams) of the solid content excluding the colorant of the photosensitive composition and the number of moles M of carboxyl groups contained in the solid content excluding the colorant of the photosensitive composition is 1300 or more and 1600 or less. Satisfaction is important from the viewpoint of film stability and processability after application, and shape maintenance of the uneven portion of the base substrate. As the shape retention is excellent, the display reading of the mark portion becomes good. The solid content referred to herein refers to all components excluding the organic solvent among the components contained in the photosensitive composition.

The number of moles M of carboxyl groups contained in the solid content excluding the colorant of the photosensitive composition can be calculated from the amount of carboxylic acid in each raw material to be blended, and can be specifically measured by the following method. First, the photosensitive composition is measured, the number of moles of the acid component is measured using an automatic potential difference measuring device, etc., and the number of moles of the acid component contained in the solid content excluding the colorant of the photosensitive composition can be determined. For the acid components required for neutralization, each component is isolated and purified by methods such as preparative GPC, preparative HPLC, and column purification, and subjected to ¹ H-NMR, ¹³ C-NMR, two-dimensional NMR such as HMBC and HMQC, IR, etc. It can be identified by calculating the number of moles of the carboxyl group among the number of moles of the acid component. Here, when an acid component is present in components not included in the solid content such as an organic solvent, the number of moles of those acid components is subtracted to calculate the number of moles M of the carboxyl group contained in the solid content excluding the colorant of the photosensitive composition. .

If T/M is less than 1300, film stability after application deteriorates. T/M is preferably 1320 or more, more preferably 1350 or more, and still more preferably 1400 or more. Additionally, if T/M is greater than 1600, the shape maintenance of the uneven portion of the underlying substrate deteriorates. T/M is preferably 1590 or less, more preferably 1580 or less, further preferably 1550 or less, and even more preferably 1500 or less.

In the photosensitive composition of the present invention, when the solid content concentration is changed from 18 mass% to 25 mass%, the viscosity change amount Δη per solid content change mass ΔW, that is, Δη/ΔW, is 0.50 or more and 0.70 or less for the uneven portion of the base substrate. This is desirable from the viewpoint of shape maintenance and discharge port occlusion of the discharge device. The viscosity change amount Δη per solid content change amount ΔW referred to here can be calculated by the following method. First, prepare two types of photosensitive compositions S1 and S2, which have the same solid composition and differ only in the mixing ratio of the mixed or single organic solvent, and whose solid concentrations are W1 and W2, respectively (unit: mass%. However, W1>W2), and its viscosity is said to be η1 and η2 (unit: cP), respectively. In this case, the viscosity change amount Δη per solid content change amount ΔW is (η1-η2)/(W1-W2). Viscosity refers to the measured value with an E-type viscometer at a temperature of 23°C. The viscosity change amount Δη per solid content change amount ΔW is preferably 0.50 or more, more preferably 0.53 or more, and even more preferably 0.56 or more from the viewpoint of shape maintenance for the uneven portion of the base substrate. In addition, the viscosity change amount Δη per solid content change amount ΔW is preferably 0.70 or less, more preferably 0.64 or less, and still more preferably 0.60 or less from the viewpoint of the discharge port blocking property of the discharge device.

(Method for producing photosensitive composition)

The method for producing the photosensitive resin composition of the present invention is not particularly limited, and it can be produced by a general-purpose method. For example, in a container such as a flask or a reaction furnace, a dispersion containing the alkali-soluble resin having the tricyclodecanyl skeleton, the radical polymerizable compound, a photopolymerization initiator, a colorant, and optionally other additives and an organic solvent. It can be obtained by adding and stirring. At this time, a solution in which each component is diluted with an organic solvent or a solution in which each component is dissolved in an organic solvent may be used. The order in which each component is added may be any, and the obtained photosensitive composition may be filtered.

(Color filter board, fingerprint sensor)

Next, the color filter substrate and fingerprint sensor of the present invention will be described. The color filter substrate of the present invention has a pixel containing a photocured product of the photosensitive composition of the present invention. Additionally, the fingerprint sensor of the present invention has a photocured product of the photosensitive composition of the present invention. Additionally, the color filter substrate or fingerprint sensor of the present invention may include a black matrix, a photo spacer, an overcoat layer, an alignment film, a polarizing plate, a retardation plate, an anti-reflection film, a transparent electrode, a diffusion plate, etc.

Substrates used in the color filter substrate or fingerprint sensor of the present invention include, for example, soda glass, alkali-free glass, borosilicate glass, quartz glass, aluminoborosilicate glass, aluminosilicate glass, alkali aluminosilicate glass, and surfaces made of silica. Examples include plates of inorganic glass such as coated soda-lime glass, silicon wafers, and films and sheets of organic plastic. Two or more types of these may be stacked. Additionally, when the display device provided with the color filter substrate of the present invention is a reflective display device or a display device having a light-emitting element such as silicon OLED, the substrate may be opaque.

The organic plastic film or sheet may be a self-supporting film or, for example, a film formed by coating on a substrate such as a glass substrate. In the case of such a coating film, peeling can be achieved by appropriately adjusting the adhesion between the substrate and the film using a laser or the like. Examples of organic plastic materials include polypropylene, polyethylene, polystyrene, polyester such as polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyimide, polyamide, polyamideimide, polyethersulfone, and polyester. Examples include fluorine-containing polymers such as tetrafluoroethylene (PTFE), polyether ether ketone, polyphenylene ether, polyarylate, and polysulfone.

From the viewpoint of substrate strength, the substrate is preferably a film with a thickness of 5 μm or more, and more preferably 10 μm or more. Meanwhile, from the viewpoint of flexibility, it is preferable that the substrate be a film with a thickness of 100 μm or less.

Examples of pixels include colored pixels such as red and blue, and transparent pixels. Examples of the material constituting the pixel include the photosensitive composition of the present invention and a colored photosensitive composition containing a binder resin such as an acrylic resin or polyimide resin and a radically polymerizable compound. From the viewpoint of improving color purity, the pixel film thickness is preferably 0.5 μm or more, more preferably 1.0 μm or more, and still more preferably 1.4 μm or more. On the other hand, from the viewpoint of improving the flatness, pattern processability, and reliability of the color filter substrate, 3.0 μm or less is preferable, and 2.8 μm or less is more preferable. Additionally, in order to improve the reading performance of the fingerprint sensor, a large-sized coloring member can be formed from a member containing the photosensitive composition of the present invention.

The black matrix prevents a decrease in contrast and color purity due to light leakage between pixels, and is preferably disposed between pixels or in a frame portion. Examples of the material constituting the black matrix include a photosensitive composition containing a binder resin such as an acrylic resin or polyimide resin and a radically polymerizable compound, a non-photosensitive resin composition colored black, etc. There is no particular designation on the film thickness of the black matrix, but from the viewpoint of light blocking properties, 0.5 μm or more is preferable, and 1.0 μm or more is more preferable.

The photo spacer formed on the color filter substrate provides a certain gap between opposing substrates, and the gap can be filled with a liquid crystal compound or the like. Therefore, the process of arranging spacers can be omitted when manufacturing a liquid crystal display device. The photo spacer is preferably fixed to a specific location on the color filter substrate so as to be in contact with the opposing substrate when the liquid crystal display device is manufactured. Examples of the material constituting the photo spacer include a photosensitive composition containing a binder resin such as acrylic resin or polyimide resin and a radically polymerizable compound. The shape of the photo spacer includes, for example, a columnar shape, a prismatic shape, a truncated cone shape, and a truncated pyramid shape. The diameter and height of the photo spacer are not specifically specified, and any may be used.

The overcoat layer suppresses the transmission of impurities from the pixels of the color filter substrate or flattens the level difference between the pixels of the color filter substrate. Examples of the material constituting the overcoat layer include epoxy resin, acrylic epoxy resin, acrylic resin, siloxane resin, polyimide resin, and photosensitive or non-photosensitive materials commercially available as planarizing materials.

Materials constituting the transparent electrode include, for example, metals such as aluminum, chromium, tantalum, titanium, neodymium, or molybdenum, indium-tin-oxide (ITO), and indium-zinc-oxide (Indium-Tin-Oxide). Zinc-Oxide (InZnO), etc. may be mentioned.

(Color filter substrate, fingerprint sensor manufacturing method)

As a method of manufacturing a color filter substrate or a fingerprint sensor, for example, a method of forming a pattern of a pixel containing a resin composition on a substrate is included. Below, the manufacturing method is explained by taking a color filter substrate having pixels containing the photosensitive composition of the present invention as an example. The photosensitive composition of the present invention is applied onto a substrate, patterned through selective exposure and development using a photomask, and fired to form members such as pixels and obtain a color filter substrate.

Methods for applying the photosensitive composition of the present invention on a substrate include, for example, spin coater, bar coater, blade coater, roll coater, die coater, inkjet printing method, screen printing method, method of immersing the substrate in the photosensitive composition, photosensitive coating method, etc. A method of spraying the composition on a substrate may be included.

Subsequently, the substrate coated with the photosensitive composition is dried to form a coating film of the photosensitive composition on the substrate. Examples of drying methods include air drying, heat drying, and vacuum drying. You may combine two or more types of these, and for example, it is preferable to dry under reduced pressure followed by heat drying. The temperature of heat drying is preferably 80 to 130°C, and the heat drying device is preferably a hot air oven or hot plate. Additionally, in the case of a color filter substrate having a black matrix, it is preferable to form a coating film of the photosensitive composition on the substrate on which the black matrix has been previously formed.

Next, a photomask is placed on the coating film of the photosensitive composition, and exposure is selectively performed. Examples of exposure machines include proximity exposure machines, mirror projection exposure machines, lens scan exposure machines, and steppers. From the viewpoint of precision, a lens scan exposure machine is preferred. In addition, examples of light sources used for exposure include ultra-high pressure mercury lamps, chemical lamps, and high-pressure mercury lamps.

Afterwards, the unexposed areas are removed by development using an alkaline developer, and a coating film pattern is formed. Examples of alkaline substances used in alkaline developers include 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, and organic alkalis such as tetramethylammonium hydroxide. Examples of the alkaline developer include 0.02 to 1% by mass of potassium hydroxide or tetramethylammonium hydroxide.

Thereafter, the obtained coating film pattern is heat-treated to obtain a color filter substrate with patterned pixels. The heat treatment may be performed in air, nitrogen atmosphere, or vacuum. The heating temperature is preferably 80 to 250°C. The heating time is preferably 5 minutes to 5 hours. As a heat processing device, a hot air oven and a hot plate are preferable. The heat treatment may be performed continuously or stepwise.

For each pixel of 3 to 6 colors included in the color filter substrate, pixel formation is performed sequentially by the above method. The formation order of each color is not particularly limited, but when forming a pixel containing a dye, it is preferable to form the pixel containing the dye after forming other pixels from the viewpoint of further suppressing color transfer of the color material.

(display device)

The color filter substrate of the present invention can be used as a component of display devices such as liquid crystal displays, organic EL displays, and electronic paper, and can be used as image display devices. That is, the display device of the present invention has the color filter substrate of the present invention. Additionally, the display device may have a light source such as an external light source, or various films such as a brightness enhancing film or a diffusion plate. A display device refers to a device that displays an image by making part of the screen visible. Examples of the display device include a transmissive liquid crystal display, a transflective liquid crystal monitor, a reflective liquid crystal display, an organic EL display, an inorganic EL display, a quantum dot display, and electronic paper. Reflective display devices include devices that display with outdoor or indoor light, such as wearable terminals, electronic signs, digital signage, and electronic price tags for shelves.

The display device of the present invention is a display device having a fingerprint sensor having a photocured product of the photosensitive composition of the present invention. A display device with a fingerprint sensor as used herein is a display device in which a fingerprint sensor is installed on the image display surface of an image display device and has a function of detecting a fingerprint by placing a finger on the image display portion. As the fingerprint sensor, a known fingerprint sensor can be used. By disposing a plurality of authentication sensors in the image display device, the position at which the fingerprint is detected is not limited to a specific position, and detection of the fingerprint at a plurality of positions in the image display portion becomes possible.

(Manufacturing method of display device)

As an example of a method for manufacturing a display device of the present invention, a method for manufacturing a liquid crystal display device having a color filter substrate is shown below. The color filter substrate and the array substrate of the present invention are opposed to each other and bonded together through a liquid crystal alignment film provided on the substrates and a spacer for maintaining the cell gap. Additionally, a TFT liquid crystal display device or a TFD liquid crystal display device can be manufactured by providing a thin film transistor (TFT) element, a thin film diode (TFD) element, a scanning line, or a signal line, etc. on an array substrate. Next, after the liquid crystal is injected from the injection port provided in the seal portion, the injection port is sealed. Additionally, the liquid crystal display device is completed by installing a backlight and mounting an IC driver, etc. Additionally, as a backlight, 2-wavelength LED, 3-wavelength LED, or CCFL can be used, but 3-wavelength LED is preferable because the color reproduction range of the liquid crystal display device can be expanded and power consumption can be kept low. do.

Example

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. First, the evaluation method in Examples and Comparative Examples will be described. In addition, other components used in each Example and Comparative Example are as follows.

radically polymerizable compounds

C1: Pentaerythritol triacrylate (does not have a carboxyl group in the structure)

photopolymerization initiator

D1: “Adeka Ackles” (registered trademark) NCI831 (manufactured by ADEKA Co., Ltd., does not have a carboxyl group in the structure)

organic solvent

E1: Propylene glycol monomethyl ether acetate.

<Shape maintenance evaluation>

As shown in Figure 1, the photosensitive compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were placed on a glass substrate having a pattern shape containing the coloring composition with a length of 400 μm, a width of 40 μm, and a height of 1.5 μm. , was applied to cover the pattern so that the film thickness at a location 200 μm away from the pattern end was 2.5 μm, and dried at 90°C for 10 minutes to form a film containing the photosensitive composition. The height H and the inclination width L of the resting portion of the pattern were measured using a laser microscope VK-9710 manufactured by Keyence Co., Ltd., and shape retention was evaluated. The closer the height H is to 2.5 μm and the closer the inclination width L is to 0 μm, the better the shape retention is.

<Film stability evaluation>

The photosensitive compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were applied on a glass substrate and dried at 90°C for 10 minutes to prepare two glass substrates with film formation. One prepared sheet was exposed to i-line 40mJ/cm2 through a photomask with a 50㎛ line & space pattern. Next, shower development was performed for 70 seconds with a 0.15% by mass tetramethylammonium hydroxide aqueous solution at 23°C, and then washed with pure water. It was fired at 230°C for 30 minutes to obtain Substrate 1 with a 2.3㎛ thick film. Of the two prepared glass substrates on which the film was formed, the remaining one was left at a temperature of 23°C for 48 hours and then exposed to i-line 40mJ/cm2 through a photomask with a 50㎛ line & space pattern. . Next, shower development was performed for 70 seconds with a 0.15% by mass tetramethylammonium hydroxide aqueous solution at 23°C, and then washed with pure water. By firing at 230°C for 30 minutes, Substrate 2 with a 2.3㎛ thick film was obtained. The line widths of the 50 μm patterns of Substrate 1 with a coating film and Substrate 2 with a coating film were measured using an optical microscope and evaluated based on the following evaluation criteria.

A: Line width change in 48 hours is less than 1㎛

B: Line width change in 48 hours is 1㎛ or more and less than 2㎛

C: Line width change in 48 hours is more than 2㎛ or residue occurs on the glass part.

<Evaluation of occlusion>

The photosensitive compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were applied on a glass substrate using a slit coater with a gap between the spindles of 100 μm. After completion of application, it was left to stand for 6 minutes and applied to another glass substrate. The obtained substrate was visually observed and evaluated based on the following evaluation criteria.

A: No uneven application.

B: Vertical stripes are uneven.

Preparation Example 1 (Preparation of dispersion (A1))

C.I. Pigment Green 58 ("FASTGEN" (registered trademark) Green A110, manufactured by DIC Corporation) 150 g, "BYK" (registered trademark) LPN6919 (manufactured by Big Chemistry, Inc., polymer dispersant solution (60 mass% propylene glycol monomethyl ether solution)) A slurry was prepared by mixing 125 g of "Cyclomer" (registered trademark) ACA250 (manufactured by Daicel Chemical Co., Ltd., 45 mass% dipropylene glycol monomethyl ether solution), and 625 g of propylene glycol monomethyl ether (PMA). . The beaker containing the slurry was connected to a dyno mill and a tube, and dispersion treatment was performed for 8 hours at a peripheral speed of 14 m/s using zirconia beads with a diameter of 0.5 mm as a medium, and C.I. Pigment Green 58 dispersion (A1) was prepared. Additionally, dispersion (A1) does not have a carboxyl group.

Preparation Example 2 (Preparation of dispersion (A2))

C.I. Instead of Pigment Green 58, C.I. Production Example 1 was repeated except that 150 g of Pigment Yellow 150 (“Chromofine (registered trademark) Yellow 6266EC” manufactured by Dainichi Seka Co., Ltd.) was used, and C.I. Pigment Yellow 150 dispersion (A2) was prepared. Additionally, dispersion (A2) does not have a carboxyl group.

Preparation Example 3 (Synthesis of alkali-soluble resin solution (B1))

Polymerize 20 g of methacrylic acid, 20 g of styrene, 8 g of tricyclodecanyl methacrylate, 20 g of methyl methacrylate, 3 g of 2,2'-azobis(2-methylbutyronitrile) and 150 g of PGMEA. It was placed in a container and stirred at 90°C for 2 hours under a nitrogen atmosphere, then the liquid temperature was raised to 100°C and the reaction was allowed to proceed for another 5 hours. Next, the polymerization vessel was purged with air, and 10 g of glycidyl methacrylate, 1.2 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the obtained reaction solution, and the mixture was stirred at 110°C for 6 hours. The obtained solution was diluted by adding PGMEA to obtain an alkali-soluble resin solution (B1) with a solid content of 35% by mass (double bond equivalent of alkali-soluble resin 1171 g/mol, weight ratio of unit having tricyclodecanyl skeleton 9.7% by mass) , only carboxyl as the acid component). The acid value of the alkali-soluble resin was measured for a 0.1 mol/L potassium hydroxide/ethanol solution using an automatic potential difference measuring device AT-610 manufactured by Kyoto Denshi Kogyo Co., Ltd., and the acid value was 109.2 (mgKOH/g). Additionally, the weight average molecular weight in terms of polystyrene was calculated using a GPC device, and the weight average molecular weight was 31,400.

Preparation Example 4 (Synthesis of alkali-soluble resin solution (B2))

Polymerize 20 g of methacrylic acid, 20 g of styrene, 15 g of tricyclodecanyl methacrylate, 20 g of methyl methacrylate, 3 g of 2,2'-azobis(2-methylbutyronitrile) and 150 g of PGMEA. It was placed in a container and stirred at 90°C for 2 hours under a nitrogen atmosphere, then the liquid temperature was raised to 100°C and the reaction was allowed to proceed for another 5 hours. Next, the polymerization vessel was purged with air, and 9 g of glycidyl methacrylate, 1.2 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the obtained reaction solution, and stirred at 110°C for 6 hours. The obtained solution was diluted by adding PGMEA to obtain an alkali-soluble resin solution (B2) with a solid content of 35% by mass (double bond equivalent of alkali-soluble resin 1396 g/mol, weight ratio of unit having a tricyclodecanyl skeleton 17.0% by mass) , only carboxyl as the acid component). The acid value of the alkali-soluble resin was measured for a 0.1 mol/L potassium hydroxide/ethanol solution using an automatic potential difference measuring device AT-610 manufactured by Kyoto Denshi Kogyo Co., Ltd., and the acid value was 106.8 (mgKOH/g). Additionally, the weight average molecular weight in terms of polystyrene was calculated using a GPC device, and the weight average molecular weight was 12,000.

Preparation Example 5 (Synthesis of alkali-soluble resin solution (B3))

Polymerize 27 g of methacrylic acid, 15 g of styrene, 5 g of tricyclodecanyl methacrylate, 15 g of methyl methacrylate, 3 g of 2,2'-azobis(2-methylbutyronitrile) and 150 g of PGMEA. It was placed in a container and stirred at 90°C for 2 hours under a nitrogen atmosphere, then the liquid temperature was raised to 100°C and the reaction was allowed to proceed for another 5 hours. Next, the polymerization vessel was purged with air, and 13 g of glycidyl methacrylate, 1.2 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the obtained reaction solution, and stirred at 110°C for 6 hours. The obtained solution was diluted by adding PGMEA to obtain an alkali-soluble resin solution (B3) with a solid content of 35% by mass (double bond equivalent of alkali-soluble resin 868 g/mol, weight ratio of unit having tricyclodecanyl skeleton 6.3% by mass) , only carboxyl as the acid component). The acid value of the alkali-soluble resin was measured for a 0.1 mol/L potassium hydroxide/ethanol solution using an automatic potential difference measuring device AT-610 manufactured by Kyoto Denshi Kogyo Co., Ltd., and the acid value was 157.1 (mgKOH/g). Additionally, the weight average molecular weight in terms of polystyrene was calculated using a GPC device, and the weight average molecular weight was 28,900.

Preparation Example 6 (Synthesis of alkali-soluble resin solution (B4))

Polymerize 20 g of methacrylic acid, 20 g of styrene, 7 g of tricyclodecanyl methacrylate, 20 g of methyl methacrylate, 3 g of 2,2'-azobis(2-methylbutyronitrile) and 150 g of PGMEA. It was placed in a container and stirred at 90°C for 2 hours under a nitrogen atmosphere, then the liquid temperature was raised to 100°C and the reaction was allowed to proceed for another 5 hours. Next, the polymerization vessel was purged with air, and 14 g of glycidyl methacrylate, 1.2 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the obtained reaction solution, and the mixture was stirred at 110°C for 6 hours. The obtained solution was diluted by adding PGMEA to obtain an alkali-soluble resin solution (B4) with a solid content of 35% by mass (double bond equivalent of alkali-soluble resin 867g/mol, weight ratio of unit having tricyclodecanyl skeleton 8.2% by mass) , only carboxyl as the acid component). The acid value of the alkali-soluble resin was measured for a 0.1 mol/L potassium hydroxide/ethanol solution using an automatic potential difference measuring device AT-610 manufactured by Kyoto Denshi Kogyo Co., Ltd., and the acid value was 87.6 (mgKOH/g). Additionally, the weight average molecular weight in terms of polystyrene was calculated using a GPC device, and the weight average molecular weight was 32,300.

(Example 1)

In a 50 mL plastic bottle, 6.11 g of dispersion A1 obtained in Production Example 1, 2.04 g of dispersion A2 obtained in Production Example 2, 4.42 g of alkali-soluble resin solution B1 obtained in Production Example 3, 1.57 g of radical polymerizable compound C1, and photopolymerization. 0.09 g of initiator D1 and 15.78 g of organic solvent E1 were added and stirred for 3 hours to prepare a photosensitive composition (F1, T/M = 1387). The obtained photosensitive composition was evaluated for shape retention by the above method. As a result, the height H of the resting portion with respect to the pattern was 1.30 μm, and the slope width L was 17.3 μm. Additionally, when film stability was evaluated using the above method, the change in line width at 48 hours was less than 1 μm (A evaluation). Additionally, when occlusiveness was evaluated by the above method, no uneven coating was observed on the substrate (A evaluation). Additionally, only the mixing amount of the organic solvent E1 was changed to prepare a 25% by mass photosensitive composition that differed only in solid concentration from the photosensitive composition (F1, 18% by mass of solids), and each viscosity was measured using a viscosity meter RE manufactured by Dokki Sangyo Co., Ltd. Measured at -215L, the viscosity change amount Δη/ΔW per solid content change when the solid content concentration was changed from 18 mass% to 25 mass% was evaluated, and it was 0.58.

(Examples 2 to 7, Comparative Examples 1 to 4)

Photosensitive compositions (F2 to F11) were obtained in the same manner as in Example 1, except that the types and amounts of the dispersion, alkali-soluble resin solution, radical polymerizable compound, photopolymerization initiator, and organic solvent were changed as shown in Table 1. Using the obtained photosensitive composition, the results evaluated by the above method are summarized in Table 2.

1: Glass substrate
2: Pattern shape
3: Film containing photosensitive composition
L: slope width
H: height
[Industrial applicability]
The photosensitive composition of the present invention can be suitably used for color filter substrates, fingerprint sensors and display devices equipped therewith, decorative ink materials, etc.

Claims (9)

A photosensitive composition containing an alkali-soluble resin having a tricyclodecanyl skeleton, a radically polymerizable compound, a photopolymerization initiator, a colorant, and an organic solvent, wherein the alkali-soluble resin having a tricyclodecanyl skeleton accounts for 20% by mass of the solid content. It is 40% by mass or less, and the ratio T/M of the total mass Tg of the solid content excluding the colorant of the photosensitive composition and the number of moles M of carboxyl groups contained in the solid content excluding the colorant of the photosensitive composition satisfies 1300 or more and 1600 or less. Photosensitive composition. The method according to claim 1, wherein the weight ratio of the unit having a tricyclodecanyl skeleton contained in the alkali-soluble resin having a tricyclodecanyl skeleton is 2% by mass or more and 15% by mass of the alkali-soluble resin having a tricyclodecanyl skeleton. % or less of the photosensitive composition. The photosensitive composition according to claim 1 or 2, wherein the alkali-soluble resin having a tricyclodecanyl skeleton has a weight average molecular weight of 20,000 to 40,000. The photosensitive composition according to claim 1 or 2, wherein the alkali-soluble resin having a tricyclodecanyl skeleton has a double bond equivalent weight of 500 or more and 2,000 or less. The photosensitive composition according to claim 1 or 2, wherein the viscosity change amount Δη (cP) per solid content change mass ΔW (mass%) when the solid content concentration is changed from 18 mass% to 25 mass% is 0.50 or more and 0.70 or less. A color filter substrate having a pixel containing a photocured product of the photosensitive composition according to claim 1 or 2. A fingerprint sensor comprising a photocured product of the photosensitive composition according to claim 1 or 2. A display device comprising the color filter substrate according to claim 6. A display device having the fingerprint sensor according to claim 7.