WO2023021986A1

WO2023021986A1 - Photosensitive composition, color filter substrate, fingerprint sensor, and display device

Info

Publication number: WO2023021986A1
Application number: PCT/JP2022/029742
Authority: WO
Inventors: 小田拓郎
Original assignee: 東レ株式会社
Priority date: 2021-08-20
Filing date: 2022-08-03
Publication date: 2023-02-23
Also published as: KR20240044426A; CN117716293A; JPWO2023021986A1

Abstract

Provided is a photosensitive composition that has excellent shape-holding properties for uneven sections of a base substrate and also has little change in treatment properties when left for a long time after coating. The photosensitive composition contains an alkali-soluble resin that has a tricyclodecanyl skeleton, a radically polymerizable compound, a photoinitiator, a coloring material, and an organic solvent. The proportion of the alkali-soluble resin having the tricyclodecanyl skeleton is 20%–40% by mass of the solid content. The ratio T/M between the total mass Tg of the solid content of the photosensitive composition excluding the coloring material and the number of mols M of carboxyl groups in the solid content of the photosensitive composition excluding the coloring material is 1,300–1,600.

Description

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

The present invention relates to a photosensitive composition, a color filter substrate, a fingerprint sensor and a display device.

Liquid crystal display devices are used in various applications such as televisions, laptop computers, personal digital assistants, smartphones, digital cameras, etc., taking advantage of their characteristics such as lightness, thinness, and low power consumption. Liquid crystal display devices are required to have three to six optimum colors depending on the application, and color filter substrates are used to provide various color performances.

A color filter substrate is generally manufactured by applying a photosensitive composition to the substrate with a slit coater when forming colored pixels, drying, and then exposing, developing, and baking the composition. Various photosensitive compositions are known as photosensitive compositions for color filters (see, for example, Patent Documents 1 and 2). These photosensitive compositions are applied onto a substrate and then exposed and developed using a photolithography mask to form a pattern into a desired shape.

WO2017/164127 WO2018/151044

In general, when exposing a photosensitive composition on a substrate, a pattern with 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 colored composition or the like is used as a reference.

However, when the photosensitive composition is applied to the substrate including the alignment mark, the above-mentioned photosensitive composition has low shape retention on the substrate, so even if the alignment mark is observed from above the substrate using a camera, , there was a problem that the position could not be specified.

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

An object of the present invention is to provide a photosensitive composition that is excellent in shape retention with respect to uneven portions of a base substrate, and that changes in processing characteristics is small even when left to stand after coating.

The present invention provides a photosensitive composition containing an alkali-soluble resin having a tricyclodecanyl skeleton, a radically polymerizable compound, a photopolymerization initiator, a coloring material and an organic solvent, wherein the alkali The soluble resin accounts for 20% by mass or more and 40% by mass or less in the solid content, and is contained in the total mass Tg of the solid content excluding the coloring material of the photosensitive composition and the solid content of the photosensitive composition The photosensitive composition satisfies a ratio T/M of the number of moles M of carboxyl groups of 1,300 or more and 1,600 or less.

According to the photosensitive composition of the present invention, it is possible to provide a photosensitive composition that is excellent in shape retention with respect to uneven portions of a base substrate, and that changes in processing characteristics are small even when left to stand after coating.

FIG. 2 is a cross-sectional view when a film made of a photosensitive composition is formed on a glass substrate having a pattern in the shape retention evaluation described in Examples, and shows the height H and the width L of the portion that runs over the pattern. is.

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 coloring material and an organic solvent, The proportion of the alkali-soluble resin having a nil skeleton is 20% by mass or more and 40% by mass or less in the solid content, and the total mass Tg of the solid content excluding the coloring material of the photosensitive composition and the color of the photosensitive composition The photosensitive composition satisfies a ratio T/M of 1,300 to 1,600 in terms of the number of moles M of carboxyl groups contained in the solid content excluding the material. The photosensitive composition of the present invention is excellent in shape retention with respect to uneven portions of an underlying substrate, and can suppress changes in processing characteristics even when left to stand after coating. In addition, since the photosensitive composition of the present invention is excellent in shape retention, when the photosensitive composition is applied onto a substrate including alignment marks, the film formed on the alignment marks maintains a raised shape. Therefore, even if the alignment mark is observed from above the substrate using a camera, the position can be specified.

(Alkali-soluble resin having a 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 workability and shape retention with respect to the irregularities of the base substrate, and can suppress changes in workability even when left to stand after coating.

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, polyamideimide resins, polyester resins, and polyolefin resins. etc. You may contain 2 or more types of these. From the viewpoint of stability, acrylic resin is preferably used.

For acrylic resins, ethylenically unsaturated compounds having a tricyclodecanyl skeleton include, for example, tricyclodecanyl (meth)acrylate and tricyclodecanedimethanol di(meth)acrylate. Copolymers are preferred.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylacetic acid, and acid anhydrides thereof. You may use 2 or more types 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, in the alkali-soluble resin having a tricyclodecanyl skeleton, from the viewpoint of shape retention with respect to the irregularities of the underlying substrate. Below, more preferably 15% by mass or less, still more preferably 12% by mass or less. In addition, from the viewpoint of the stability of the film after coating, the weight ratio of the unit having a tricyclodecanyl skeleton contained in the alkali-soluble resin having a tricyclodecanyl skeleton is It is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more. In addition, from the viewpoint of the discharge port clogging property 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, in the alkali-soluble resin. is.

The weight ratio of the unit having a tricyclodecanyl skeleton can be determined by calculating the weight of each structural unit from the molar ratio of each structural unit in the alkali-soluble resin having a tricyclodecanyl skeleton. Moreover, 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, each component contained in the photosensitive composition of the present invention is isolated and purified by methods such as preparative GPC, preparative HPLC, and column purification, and the structure of an alkali-soluble resin having a tricyclodecanyl skeleton is obtained. can be analyzed and calculated. Regarding the structural analysis of the 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 and HMQC, and the like. , can be calculated by calculating the weight ratio of the tricyclodecanyl skeleton in the total alkali-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, ( sec-butyl meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, etc. unsaturated carboxylic acid alkyl esters, styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, aromatic vinyl compounds such as α-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, glycidyl Unsaturated carboxylic acid glycidyl esters such as acrylates and glycidyl methacrylate, carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile, 1,3-butadiene, isoprene and macromonomers such as polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polysilicone having (meth)acryloyl groups at their terminals. You may use 2 or more types of these.

From the viewpoint of film stability after coating, the alkali-soluble resin having a tricyclodecanyl skeleton preferably has an ethylenically unsaturated group in the side chain. Examples of ethylenically unsaturated groups include vinyl groups, allyl groups, acrylic groups, and methacrylic groups. Examples of the acrylic resin having an ethylenically unsaturated group in the side chain include "Cychromer" (registered trademark) P (Daisel Chemical Industries, Ltd.), alkali-soluble cardo resin, and the like.

The double bond equivalent 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 the stability and workability of the film after coating. be. In addition, the double bond equivalent 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, workability, and reliability with respect to the irregularities of the underlying substrate. 000 or less, more preferably 1,500 or less.

The weight-average molecular weight of the alkali-soluble resin having a tricyclodecanyl skeleton is preferably 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, more preferably 9,000 or more, from the viewpoint of the strength of the cured film. In addition, from the viewpoint of shape retention with respect to uneven portions of the base substrate, it is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more. Further, from the viewpoint of stability of the photosensitive composition, compatibility with other components, and stability of the film after coating, the weight average molecular weight of the alkali-soluble resin having a tricyclodecanyl skeleton is preferably 200,000 or less. It is more preferably 100,000 or less, still more preferably 40,000 or less. From the viewpoint of clogging of 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, more preferably 35,000 or less. The weight average molecular weight of the alkali-soluble resin referred to here refers to a standard polystyrene equivalent 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 the solid content. If the content of the alkali-soluble resin having a tricyclodecanyl skeleton is less than 20% by mass in the solid content, the shape retainability of the underlying substrate with respect to the irregularities deteriorates. The content of the alkali-soluble resin having a tricyclodecanyl skeleton is more preferably 22% by mass or more, and even more preferably 25% by mass or more. Moreover, when the content of the alkali-soluble resin having a tricyclodecanyl skeleton is more than 40% by mass in the solid content, the stability of the coated film deteriorates. The content of the alkali-soluble resin having a tricyclodecanyl skeleton is preferably 35% by mass or less, more preferably 30% by mass or less, in the solid content. Moreover, from the viewpoint of clogging of the ejection port of the ejection device, the content of the alkali-soluble resin having a tricyclodecanyl skeleton is preferably 35% by mass or less, more preferably 32% by mass or less in the solid content.

(Radical polymerizable compound)
The photosensitive composition of the invention contains a radically polymerizable compound. The term "radical polymerizable compound" as used herein refers to a compound that reacts by radical polymerization, and refers to a compound having 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 unsaturated hydrocarbon groups include (meth)acryloyl groups, vinyl groups, and maleimide groups. You may have 2 or more types of these.

Examples of radically polymerizable compounds include dipentaerythritol penta(meth)acrylate, tetratrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, penta(meth)acryloyloxy Dipentaerythritol monosuccinic acid ester, ethylene oxide-modified or propylene oxide-modified products such as dipentaerythritol hexa(meth)acrylate, styrene derivatives, polyfunctional maleimide compounds, poly(meth)acrylate carbamate, 1,6-hexane adipic acid Oligomers such as diol (meth)acrylate, propylene oxide (meth)acrylate phthalate anhydride, diethylene glycol (meth)acrylate trimellitate, rosin-modified epoxy di(meth)acrylate, and alkyd-modified (meth)acrylate, Bifunctional (meth)acrylates such as propylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, triacrylic formal, bisphenoxyethanol fluorene diacrylate, dicyclo Pentanedienyl diacrylate, alkyl modified products thereof, alkyl ether modified products, alkyl ester modified products and the like are included. You may contain 2 or more types of these. Pentaerythritol triacrylate is preferably used as the radically polymerizable compound from the viewpoint of film stability after coating.

The content of the radically polymerizable compound in the photosensitive composition of the present invention is preferably 40% by mass or more in the solid content from the viewpoint of patterning properties. On the other hand, from the viewpoint of suppressing film thickness unevenness during film formation 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 in the solid content. The following are more preferable, and 60% by mass or less is even more preferable.

(Photoinitiator)
The photosensitive composition of the invention contains a photopolymerization initiator. By containing a photopolymerization initiator, the sensitivity at the time of 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) to generate radicals. Examples of photopolymerization initiators include oxime ester compounds, benzophenone compounds, acetophenone compounds, oxanthone compounds, anthraquinone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, carbazole compounds, and triazine compounds. compounds, phosphorus-based compounds, titanocene-based compounds, and the like.

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-tetrahydrofuranylmethoxy benzoyl)-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 Arcles” (registered trademark) N-1919, NCI-930 (manufactured by ADEKA Corporation), “IRGACURE” (registered trademark) OXE01, OXE02 (manufactured by BASF Corporation), and the like. Examples of benzophenone compounds include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone and the like. Examples of acetophenone compounds include 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[ 4-(methylthio)phenyl]-2-morpholino-1-propane, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 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) and the like. Examples of anthraquinone compounds include t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenoquinone, nanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone and the like. Examples of imidazole compounds include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer. Benzothiazole compounds include, for example, 2-mercaptobenzothiazole. Examples of benzoxazole compounds include 2-mercaptobenzoxazole. Examples of triazine-based compounds include 4-(p-methoxyphenyl)-2,6-di-(trichloromethyl)-s-triazine. You may contain 2 or more types of these.

The content of the photopolymerization initiator is preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 5% by mass of the solid content excluding the coloring material of the photosensitive composition, from the viewpoint of sensitivity, patterning properties, and processability. % or more is more preferable. On the other hand, the content of the photopolymerization initiator is preferably 30% by mass or less, preferably 20% by mass or less, in the solid content of the photosensitive composition excluding the coloring material, from the viewpoint of sensitivity, patterning properties, processability, and heat resistance. More preferably, 15% by mass or less is even more preferable.

(colorant)
The photosensitive composition of the invention contains a coloring material. Examples of the coloring material include organic pigments, inorganic pigments, dyes, and the like, and two or more of these may be contained. Among these, organic pigments and dyes are preferable from the viewpoint of further improving the transmittance.

As a red colorant, for example, C.I. I. Pigment Red (hereinafter "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 pixel luminance characteristics, PR254, PR177, and diketopyrrolopyrrole colorants having a bromine group are preferable, and from the viewpoints of brightness, vividness, and prevention of color mixing, a diketopyrrolopyrrole colorant having a bromine group is used. is preferred.

Examples of yellow colorants include organic pigments, inorganic pigments, and dyes. 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, PY153, PY154 , PY166, and PY168 (all numbers are color index numbers). You may contain 2 or more types of these. From the viewpoint of color purity, light transmittance and contrast, PY129, PY139, PY150 and PY185 are preferred, and PY150 and PY185 are more preferred.

Examples of green colorants include organic pigments, inorganic pigments, and dyes. I. Pigment Green (hereinafter “PG”) PG1, PG2, PG4, PG7, PG8, PG10, PG13, PG14, PG15, PG17, PG18, PG19, PG26, PG36, PG38, PG39, PG45, PG48, PG50, PG51, PG54 , PG55, PG58, and PG59 (all numbers are color index numbers). You may contain 2 or more types of these.

For example, C.I. I. Pigment Orange (hereinafter referred to as "PO") 13, PO31, PO36, PO38, PO40, PO42, PO43, PO51, PO55, PO59, PO61, PO64, PO65, PO71 and the like.

For example, C.I. I. Pigment Blue (hereinafter "PB") 15, PB15:3, PB15:4, PB15:6, PB21, PB22, PB60, PB64 and the like.

For example, C.I. I. Pigment Violet (hereinafter referred to as "PV") 19, PV23, PV29, PV30, PV32, PV37, PV40, PV50, etc. (all numbers are color index numbers).

Dyes include, for example, oil-soluble dyes, acid dyes, direct dyes, basic dyes, and acid mordant dyes. Alternatively, the dye may be made into a lake, or a salt-forming compound of a dye and a nitrogen-containing compound may be used.

Examples of red, green, blue, purple or yellow dyes include direct dyes, acid dyes and basic dyes. Specific examples of these dyes include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, xanthene dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilbene dyes, Examples include diarylmethane dyes, triarylmethane dyes, fluorane dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, fulgide dyes, nickel complex dyes, and azulene dyes. The dye may be dissolved in the photosensitive composition or dispersed as particles.

In order to increase the resistance to heat, light, acid, alkali or organic solvent, the basic dye is preferably a salt-forming compound composed of an organic acid such as an organic sulfonic acid or an organic carboxylic acid or a perchloric acid, such as Tobias acid. Naphthalenesulfonic acid or perchloric acid is more preferable. Similarly, salt-forming compounds comprising quaternary ammonium salts, primary to tertiary amines, or sulfonamides are preferred as acid dyes and direct dyes in order to increase resistance to heat, light, acids, alkalis, organic solvents, and the like.

The content of the coloring material 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 part of the coating device. Further, the content of the coloring material is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less in the solid content of the photosensitive composition, from the viewpoint of film stability. be.

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

In addition, the content of the coloring material in the photosensitive composition can be quantified by mass spectrometry using a MALDI mass spectrometer or a time-of-flight secondary ion mass spectrometer. From the content of the component, the ratio (% by mass) of the solid content in the photosensitive composition can be determined. In addition, when the mixing ratio of the raw materials of the photosensitive composition is known, the ratio (% by mass) of the solid content in the photosensitive composition can be calculated from the blending amount of the coloring material and the blending amount of other components. can ask.

(Organic solvent)
The photosensitive composition of the invention contains an organic solvent. Examples of organic solvents include 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-butyl acetate, 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, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary Butyl ether, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, isopentylbutanol acetate, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, cyclopentanone, cyclohexanone, xylene, ethylbenzene, solvent naphtha, etc. mentioned. You may contain 2 or more types of these.

Among the components of the organic solvent contained in the photosensitive composition of the present invention, the ratio of the organic solvent having a boiling point of 150° C. or less is 80% by mass or more, from the viewpoint of shape retention with respect to the irregularities of the underlying substrate. preferred from

(other ingredients)
The photosensitive composition of the present invention may further contain dispersants, chain transfer agents, photosensitizers, polymerization inhibitors, adhesion improvers, surfactants, cross-linking agents and the like.

(dispersant)
The photosensitive composition of the present invention may contain a dispersant such as a pigment derivative together with the colorant. Examples of dispersants include low-molecular-weight dispersants such as pigment intermediates and derivatives, and high-molecular-weight dispersants. Examples of pigment derivatives include alkylamine-modified pigment skeletons, carboxylic acid derivatives, and sulfonic acid derivatives, which contribute to appropriate wetting and stabilization of pigments. Preferred are sulfonic acid derivatives of the pigment backbone, which have a pronounced effect on stabilizing fine pigments.

Examples of polymer dispersants include polyesters, polyalkylamines, polyallylamines, polyimines, polyamides, polyurethanes, polyacrylates, polyimides, polyamideimides, and copolymers thereof. You may contain 2 or more types of these. Among these polymer dispersants, those having an amine value of 5 to 200 mgKOH/g and an acid value of 1 to 100 mgKOH/g are preferable. Among them, a polymer dispersant having a basic group is preferable, and can improve the storage stability of the pigment dispersion and the photosensitive composition. Commercially available polymer dispersants having a basic group include, for example, "Solsperse" (registered trademark) (manufactured by Avecia), "EFKA" (registered trademark) (manufactured by Efka), and "Ajisper" (registered trademark). ) (manufactured by Ajinomoto Fine-Techno Co., Ltd.) and “BYK” (registered trademark) (manufactured by BYK-Chemie Corporation). You may contain 2 or more types of these. Among them, "Solsperse" (registered trademark) 24000 (manufactured by Avecia), "EFKA" (registered trademark) 4300, 4330 (manufactured by Efka), 4340 (manufactured by Efka), "Ajisper" (registered trademark) PB821, PB822 (Ajinomoto Fine Techno Co., Ltd.), "BYK" (registered trademark) 161 to 163, 2000, 2001, 6919, 21116 (manufactured by BYK-Chemie Co., Ltd.) are preferable.

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 10 mass in solid content from the viewpoint of suppressing film thickness unevenness during film formation. % or more is preferable, 20% by mass or more is more preferable, and 30% by mass or more is even 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, more preferably 50% by mass or less, of the solid content of the photosensitive composition excluding the colorant. .

(chain transfer agent)
The photosensitive composition of the present invention may contain a chain transfer agent together with the photopolymerization initiator, thereby further improving the sensitivity. Examples of chain transfer agents include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, and 2-mercaptonicotinic 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-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), 1, 3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione), pentaerythritol tetrakis(3-mercaptopropionate), 1,4-bis(3-mercaptobutyryloxy)butane, “Karenzu” (registered trademark) MT PE-1 (manufactured by Showa Denko KK), “Karenzu” (registered trademark) MT NR-1 (Showa Denko ( (manufactured by Showa Denko Co., Ltd.), "Karenzu" (registered trademark) MT BD-1 (manufactured by Showa Denko Co., Ltd.), mercapto compounds, disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2 -Iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid and other iodinated alkyl compounds. You may contain 2 or more types of these.

(photosensitizer)
The photosensitive composition of the present invention may further contain a photosensitizer, such as a thioxanthone-based sensitizer, an aromatic or aliphatic tertiary amine, and the like. Examples of thioxanthone-based sensitizers include thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthen-9-one, "KAYACURE" (registered trademark) DETX-S (manufactured by Nippon Kayaku Co., Ltd.), and the like. mentioned. You may contain 2 or more types of these.

(Polymerization inhibitor)
The photosensitive composition of the present invention may further contain a polymerization inhibitor to improve stability. Polymerization inhibitors generally exhibit the action of inhibiting or stopping polymerization by radicals generated by heat, light, radical initiators, etc., and are generally used to prevent gelation of thermosetting resins and during polymer production. Used for polymerization termination. 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-butyl catechol and the like. You may contain 2 or more types 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, more preferably 0.005% by mass or more in the solid content. Moreover, from the viewpoint of the balance between stability and photosensitive properties, the content of the polymerization inhibitor is preferably 1% by mass or less, more preferably 0.5% by mass or less in the solid content.

(Adhesion improver)
The photosensitive composition of the present invention may further contain an adhesion improver to improve the adhesion of the coating film of the photosensitive composition to the substrate. Adhesion improvers include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-amino ethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Silane coupling agents such as trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane are included. You may contain 2 or more types of these.

(Surfactant)
The photosensitive composition of the present invention may further contain a surfactant to improve the coatability of the photosensitive composition and the uniformity of the coating film surface. Examples of surfactants include anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride; lauryldimethylamine oxide; Amphoteric surfactants such as carboxymethylhydroxyethylimidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate, fluorine-based surfactants, silicon-based surfactants, etc. is mentioned. You may contain 2 or more types 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 total mass T (grams) of the solid content of the photosensitive composition excluding the colorant and the number of moles M of carboxyl groups contained in the solid content of the photosensitive composition excluding the colorant It is important that the ratio T/M is 1300 or more and 1600 or less from the viewpoint of the stability and processability of the film after coating and the shape retention against the irregularities of the underlying substrate. Since the shape retainability is excellent, the display readability of the mark portion is improved. The term "solid content" as used herein refers to all of the components contained in the photosensitive composition, excluding the organic solvent.

The number of moles M of carboxyl groups contained in the solid content of the photosensitive composition excluding the coloring material 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. can. First, the photosensitive composition is weighed, and the number of moles of the acid component contained therein is measured by an automatic potential difference measuring device or the like, and the number of moles of the acid component contained in the solid content of the photosensitive composition excluding the coloring material. can be asked for. For acid components required for neutralization, each component is isolated and purified by methods such as preparative GPC, preparative HPLC, and column purification, followed by ¹ H-NMR, ¹³ C-NMR, two-dimensional NMR such as HMBC and HMQC, It can be identified by IR or the like, and the number of moles of the carboxyl group is calculated from the number of moles of the acid component. Here, when an acid component is present in a component that is not contained in the solid content such as an organic solvent, the number of moles of those acid components is subtracted, and the carboxyl contained in the solid content excluding the coloring material of the photosensitive composition is calculated. The number of moles M of the group can be calculated.

If the T/M is less than 1300, the stability of the film after application deteriorates. T/M is preferably 1320 or more, more preferably 1350 or more, and still more preferably 1400 or more. Further, when T/M is larger than 1600, the shape retainability to the irregularities of the base substrate is deteriorated. T/M is preferably 1590 or less, more preferably 1580 or less, still more preferably 1550 or less, and even more preferably 1500 or less.

In the photosensitive composition of the present invention, the viscosity change amount Δη per solid content change mass ΔW when the solid content concentration is changed from 18% by mass to 25% by mass, that is, Δη/ΔW is 0.50 or more and 0.70 The following is preferable from the viewpoint of shape retention with respect to the irregularities of the base substrate and discharge opening clogging property of the discharge device. The viscosity change amount Δη per solid content change amount ΔW can be calculated by the following method. First, prepare two types of photosensitive compositions S1 and S2, which have the same solid content composition of the photosensitive composition and differ only in the blending ratio of the mixed or single organic solvent, and the solid content concentrations thereof are W1 and W2 ( The unit is % by mass, where W1>W2), and the viscosities are 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 a value measured 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 still more preferably 0.56 or more from the viewpoint of shape retention with respect to 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 clogging 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 kiln, the alkali-soluble resin having a tricyclodecanyl skeleton, the radically polymerizable compound, the photopolymerization initiator, a dispersion containing a colorant, and, if necessary, the other additives , and an organic solvent are added and stirred. At this time, a solution obtained by diluting each component with an organic solvent or a dissolved solution obtained by dissolving each component with an organic solvent may be used. The components may be added in any order, and the resulting photosensitive composition may be filtered.

(color filter substrate, fingerprint sensor)
Next, the color filter substrate and fingerprint sensor of the present invention will be described. The color filter substrate of the invention has pixels containing the photocured product of the photosensitive composition of the invention. Moreover, the fingerprint sensor of the present invention has a photocured product of the photosensitive composition of the present invention. Furthermore, the color filter substrate and fingerprint sensor of the present invention may have a black matrix, photospacer, overcoat layer, alignment film, polarizing plate, retardation plate, antireflection film, transparent electrode, diffusion plate and the like.

Examples of the substrate used for the color filter substrate and the fingerprint sensor of the present invention include soda glass, non-alkali glass, borosilicate glass, quartz glass, aluminoborosilicate glass, aluminosilicate glass, alkali aluminosilicate glass, and the surface thereof. Inorganic glass plates such as silica-coated soda-lime glass, silicon wafers, organic plastic films and sheets, and the like can be used. You may laminate|stack two or more types of these. When the display device provided with the color filter substrate of the present invention is a reflective display device or a display device having light-emitting elements such as a silicon OLED, the substrate may be opaque.

The organic plastic film or sheet may be a self-supporting film or a film formed by coating on a substrate such as a glass substrate. In the case of such a coating film, the adhesive force between the substrate and the film can be appropriately adjusted by using a laser or the like, and the film can be peeled off. Examples of organic plastic materials include polypropylene, polyethylene, polystyrene, polyester such as polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyimide, polyamide, polyamideimide, polyethersulfone, polytetrafluoroethylene (PTFE), and the like. Fluorine-containing polymers, polyetheretherketones, polyphenylene ethers, polyarylates, polysulfones, and the like.

From the viewpoint of substrate strength, the substrate is preferably a film with a thickness of 5 μm or more, more preferably 10 μm or more. On the other hand, from the viewpoint of flexibility, the substrate is preferably a film having a thickness of 100 μm or less.

Pixels include colored pixels such as red and blue, and transparent pixels. Examples of the material forming 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 a polyimide resin and a radically polymerizable compound. From the viewpoint of improving color purity, the film thickness of the pixel is preferably 0.5 μm or more, more preferably 1.0 μm or more, and even more preferably 1.4 μm or more. On the other hand, it is preferably 3.0 μm or less, more preferably 2.8 μm or less, from the viewpoint of improving the flatness, pattern workability and reliability of the color filter substrate. In addition, in order to improve the reading performance of the fingerprint sensor, a colored member having a large size can be formed from a member made of the photosensitive composition of the present invention.

The black matrix prevents deterioration of contrast and color purity due to light leakage between pixels, and is preferably arranged between pixels or in the frame. Materials constituting the black matrix include, for example, a photosensitive composition containing a binder resin such as an acrylic resin or a polyimide resin and a radically polymerizable compound, and a non-photosensitive resin composition colored black. Although the film thickness of the black matrix is not particularly specified, it is preferably 0.5 μm or more, more preferably 1.0 μm or more, from the viewpoint of light shielding properties.

The photospacer formed on the color filter substrate provides a certain gap between it and the opposing substrate, and the gap can be filled with a liquid crystal compound or the like. Therefore, it is possible to omit the step of arranging the spacers when manufacturing the liquid crystal display device. The photospacer is preferably fixed at a specific location on the color filter substrate so as to be in contact with the counter substrate when the liquid crystal display device is manufactured. Materials constituting the photospacer include, for example, a photosensitive composition containing a binder resin such as an acrylic resin or a polyimide resin and a radically polymerizable compound. Examples of the shape of the photospacer include a cylindrical shape, a prismatic shape, a truncated cone shape, a truncated pyramid shape, and the like. The diameter and height of the photospacer are not particularly specified, and any one may be used.

The overcoat layer suppresses the transmission of impurities from the pixels of the color filter substrate and flattens the steps caused by the pixels of the color filter substrate. Materials constituting the overcoat layer include, for example, epoxy resins, acrylic epoxy resins, acrylic resins, siloxane resins, polyimide resins, and photosensitive or non-photosensitive materials commercially available as flattening materials.

Materials constituting the transparent electrode include, for example, metals such as aluminum, chromium, tantalum, titanium, neodymium or molybdenum, Indium-Tin-Oxide (ITO), Indium-Zinc-Oxide (InZnO), and the like.

(Manufacturing method of color filter substrate and fingerprint sensor)
As a method for manufacturing a color filter substrate or a fingerprint sensor, for example, there is a method of forming a pattern of pixels made of a resin composition on a substrate. The manufacturing method will be described below taking as an example a color filter substrate having pixels made of the photosensitive composition of the present invention. The photosensitive composition of the present invention is applied onto a substrate, patterned by selective exposure and development using a photomask, and baked to form members such as pixels, thereby obtaining a color filter substrate. .

Methods for applying the photosensitive composition of the present invention onto a substrate include, for example, a spin coater, a bar coater, a blade coater, a roll coater, a die coater, an inkjet printing method, a screen printing method, and a substrate coated with a photosensitive composition. Examples include a method of immersion and a method of spraying the photosensitive composition onto the substrate.

Subsequently, by drying the substrate coated with the photosensitive composition, a coating film of the photosensitive composition is formed on the substrate. Drying methods include, for example, air drying, heat drying, and vacuum drying. Two or more of these may be combined. For example, it is preferable to dry under reduced pressure and then heat dry. The temperature for heat drying is preferably 80 to 130° C., and the heat drying device is preferably a hot air oven or a hot plate. In the case of a color filter substrate having a black matrix, it is preferable to form a coating film of a photosensitive composition on a substrate on which a black matrix has been previously formed.

Next, a photomask is placed on the coating film of the photosensitive composition, and selective exposure is performed. Exposing machines include, for example, proximity exposure machines, mirror projection exposure machines, lens scanning exposure machines, steppers, and the like. From the viewpoint of accuracy, a lens scanning exposure machine is preferred. Light sources used for exposure include, for example, ultra-high pressure mercury lamps, chemical lamps, and high pressure mercury lamps.

After that, the unexposed areas are removed by development with an alkaline developer to form a coating film pattern. Examples of alkaline substances used in the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine and the like. Examples include primary amines, 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.

After that, by heat-treating the obtained coating film pattern, a color filter substrate having pixels patterned is obtained. The heat treatment may be performed in air, in a nitrogen atmosphere, or in vacuum. The heating temperature is preferably 80 to 250°C. The heating time is preferably 5 minutes to 5 hours. A hot air oven and a hot plate are preferable as the heat treatment device. The heat treatment may be performed continuously or stepwise.

For each pixel of 3 to 6 colors possessed by the color filter substrate, pixels are sequentially formed by the above method. The order of forming 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 coloring material.

(Display device)
The color filter substrate of the present invention can be used as a constituent element 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. Furthermore, the display device may have a light source such as an external light source, various films such as a brightness enhancement film and a diffuser plate, and the like. A display device refers to a device that displays an image by making a part of the screen visible. Examples of display devices include transmissive liquid crystal displays, transflective liquid crystal displays, reflective liquid crystal displays, organic EL displays, inorganic EL displays, quantum dot displays, and electronic paper. Examples of reflective display devices include devices that display using outdoor light or indoor light, such as wearable terminals, electronic signboards, digital signage, and electronic shelf labels.

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 having a fingerprint sensor here means a display device having a fingerprint sensor installed on the image display surface of the image display device and having a function of detecting a fingerprint by placing a finger on the image display portion. A known fingerprint sensor can be used as the fingerprint sensor. By arranging a plurality of authentication sensors in the image display device, the positions where fingerprints are detected are not limited to specific positions, and fingerprints can be detected at a plurality of positions in the image display portion.

(Manufacturing method of display device)
As an example of the method for manufacturing the display device of the present invention, a method for manufacturing a liquid crystal display device having a color filter substrate will be described below. The color filter substrate and the array substrate of the present invention are opposed to each other and bonded together via the liquid crystal alignment film provided on the substrates and the spacer for maintaining the cell gap. By providing thin film transistor (TFT) elements or thin film diode (TFD) elements, scanning lines, signal lines, etc. on the array substrate, a TFT liquid crystal display device or a TFD liquid crystal display device can be manufactured. Next, after injecting the liquid crystal from the injection port provided in the sealing portion, the injection port is sealed. Further, a liquid crystal display device is completed by attaching a backlight and mounting an IC driver and the like. As the backlight, a two-wavelength LED, three-wavelength LED, CCFL, or the like can be used, but the three-wavelength LED is preferable because the color reproduction range of the liquid crystal display device can be expanded and the power consumption can be kept low. .

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. First, evaluation methods in Examples and Comparative Examples will be described. Other components used in Examples and Comparative Examples are as follows.

Radically polymerizable compound C1: pentaerythritol triacrylate (having no carboxyl group in the structure)
Photopolymerization initiator D1: "ADEKA Arkles" (registered trademark) NCI831 (manufactured by ADEKA Corporation, having no carboxyl group in the structure.)
Organic solvent E1: propylene glycol monomethyl ether acetate.

<Shape retention evaluation>
As shown in FIG. 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 consisting of a colored composition of 400 μm in length, 40 μm in width, and 1.5 μm in height. The product was applied so as 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 of the photosensitive composition. The height H and the width of the slope L of the portion on the pattern were measured with a laser microscope VK-9710 manufactured by KEYENCE CORPORATION to evaluate the shape retainability. The closer the height H is to 2.5 μm, and the closer the slope width L is to 0 μm, the better the shape retention.

<Film stability evaluation>
The photosensitive compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were coated on glass substrates and dried at 90° C. for 10 minutes to prepare two glass substrates on which films were formed. One prepared sheet was exposed to i-rays of 40 mJ/cm ² through a photomask having a line and space pattern of 50 μm. Next, after shower development for 70 seconds with a 0.15 mass % tetramethylammonium hydroxide aqueous solution at 23° C., it was washed with pure water. It was baked at 230° C. for 30 minutes to obtain a substrate 1 with a film having a thickness of 2.3 μm. Of the two prepared glass substrates with a film formed thereon, the remaining one was allowed to stand at a temperature of 23° C. for 48 hours. ² was exposed. Next, after shower development for 70 seconds with a 0.15 mass % tetramethylammonium hydroxide aqueous solution at 23° C., it was washed with pure water. After firing at 230° C. for 30 minutes, a substrate 2 with a film having a thickness of 2.3 μm was obtained. The line width of the 50 μm pattern of the film-coated substrate 1 and the film-coated substrate 2 was measured with an optical microscope and evaluated according to the following evaluation criteria.
A: Line width change of less than 1 μm after 48 hours B: Line width change of 1 μm or more and less than 2 μm after 48 hours C: Line width change of 2 μm or more after 48 hours or residue on the glass portion.

<Evaluation of obstructiveness>
The photosensitive compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were applied onto a glass substrate using a slit coater with a gap between nozzles of 100 μm. After the application was completed, the solution was allowed to stand for 6 minutes, applied to another glass substrate, and the obtained substrate was visually observed and evaluated according to the following evaluation criteria.
A: No coating unevenness B: Vertical streak unevenness.

Production 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 BYK-Chemie, polymer dispersant solution (60% by mass propylene glycol monomethyl ether solution)) 125 g of "CYCROMER" (registered trademark) ACA250 (manufactured by Daicel Chemical Industries, Ltd., 45% by mass dipropylene glycol monomethyl ether solution) 100 g, and 625 g of propylene glycol monomethyl ether (PMA) were mixed to prepare a slurry. A beaker containing the slurry was connected to a Dyno mill with a tube, and zirconia beads with a diameter of 0.5 mm were used as media to perform dispersion treatment at a peripheral speed of 14 m/s for 8 hours. I. Pigment Green 58 dispersion (A1) was prepared. Dispersion (A1) does not have a carboxyl group.

Production Example 2 (Preparation of Dispersion (A2))
C. I. Pigment Green 58 was replaced with C.I. I. Pigment Yellow 150 (“Chromofine (registered trademark) Yellow 6266EC” manufactured by Dainichiseika Co., Ltd.) was used in the same manner as in Production Example 1 except that 150 g of C.I. I. Pigment Yellow 150 dispersion (A2) was prepared. Dispersion (A2) does not have a carboxyl group.

Production Example 3 (Synthesis of alkali-soluble resin solution (B1))
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 were charged into a polymerization vessel, After stirring at 90° C. for 2 hours under a nitrogen atmosphere, the liquid temperature was raised to 100° C., and the reaction was further performed for 5 hours. Next, the polymerization vessel was replaced with air, 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 stirred at 110° C. for 6 hours. . The resulting solution was diluted with 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, unit having a tricyclodecanyl skeleton: weight ratio of 9.7 mass %, carboxyl group only as an acid component). Using an automatic potential difference measuring device AT-610 manufactured by Kyoto Electronics Industry Co., Ltd., the acid value of the alkali-soluble resin was measured for a 0.1 mol / L potassium hydroxide ethanol solution, and the acid value was 109.2 (mg KOH / g). Further, when the polystyrene-equivalent weight average molecular weight was calculated using a GPC apparatus, the weight average molecular weight was 31,400.

Production Example 4 (Synthesis of alkali-soluble resin solution (B2))
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 were charged into a polymerization vessel, After stirring at 90° C. for 2 hours under a nitrogen atmosphere, the liquid temperature was raised to 100° C., and the reaction was further performed for 5 hours. Next, the polymerization vessel was replaced with air, 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 resulting solution was diluted with 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, unit having a tricyclodecanyl skeleton: weight ratio of 17.0% by mass, carboxyl group only as an acid component). Using an automatic potential difference measuring device AT-610 manufactured by Kyoto Electronics Industry Co., Ltd., the acid value of the alkali-soluble resin was measured for a 0.1 mol / L potassium hydroxide ethanol solution, and the acid value was 106.8 (mg KOH / g). Further, when the polystyrene equivalent weight average molecular weight was calculated using a GPC apparatus, the weight average molecular weight was 12,000.

Production Example 5 (Synthesis of alkali-soluble resin solution (B3))
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 were charged into a polymerization vessel, After stirring at 90° C. for 2 hours under a nitrogen atmosphere, the liquid temperature was raised to 100° C., and the reaction was further performed for 5 hours. Next, the polymerization vessel was replaced with air, 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 with 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, unit having a tricyclodecanyl skeleton: weight ratio of 6.3% by mass, carboxyl group only as an acid component). Using an automatic potential difference measuring device AT-610 manufactured by Kyoto Electronics Industry Co., Ltd., the acid value of the alkali-soluble resin was measured for a 0.1 mol / L potassium hydroxide ethanol solution, and the acid value was 157.1 (mg KOH / g). Further, when the polystyrene-equivalent weight average molecular weight was calculated using a GPC apparatus, the weight average molecular weight was 28,900.

Production Example 6 (Synthesis of alkali-soluble resin solution (B4))
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 were charged into a polymerization vessel, After stirring at 90° C. for 2 hours under a nitrogen atmosphere, the liquid temperature was raised to 100° C., and the reaction was further performed for 5 hours. Next, the polymerization vessel was replaced with air, 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 stirred at 110° C. for 6 hours. . The obtained solution was diluted with PGMEA to obtain an alkali-soluble resin solution (B4) with a solid content of 35% by mass (double bond equivalent of alkali-soluble resin: 867 g/mol, unit having a tricyclodecanyl skeleton: weight ratio of 8.2 mass %, only carboxyl group as an acid component). Using an automatic potential difference measuring device AT-610 manufactured by Kyoto Electronics Industry Co., Ltd., the acid value of the alkali-soluble resin was measured for a 0.1 mol / L potassium hydroxide / ethanol solution, and the acid value was 87.6 (mg KOH / g). Further, when the polystyrene-equivalent weight average molecular weight was calculated using a GPC apparatus, the weight average molecular weight was 32,300.

(Example 1)
In a 50 mL plastic bottle, 6.11 g of the dispersion A1 obtained in Production Example 1, 2.04 g of the dispersion A2 obtained in Production Example 2, 4.42 g of the alkali-soluble resin solution B1 obtained in Production Example 3, radical 1.57 g of polymerizable compound C1, 0.09 g of photopolymerization 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). When the obtained photosensitive composition was evaluated for shape retention by the method described above, the height H of the portion overlaid on the pattern was 1.30 μm, and the slope width L was 17.3 μm. Further, when the film stability was evaluated by the method described above, the change in line width after 48 hours was less than 1 μm (A evaluation). Further, when the blocking property was evaluated by the above method, no coating unevenness was observed on the substrate (A evaluation). Further, by changing only the blending amount of the organic solvent E1, a photosensitive composition (F1, solid content concentration 18 mass%) and a photosensitive composition of 25 mass% differing only in solid content concentration were prepared, and each viscosity was measured with a viscometer RE-215L manufactured by Toki Sangyo Co., Ltd., and the viscosity change amount Δη / ΔW per solid content change amount was evaluated when the solid content concentration was changed from 18% by mass to 25% by mass. As a result, it was 0.58.

(Examples 2 to 7, Comparative Examples 1 to 4)
A photosensitive composition (F2 ~F11) were obtained. Table 2 summarizes the results of evaluation by the above method using the obtained photosensitive composition.

1 Glass substrate 2 Pattern shape 3 Film L made of photosensitive composition Gradient width H Height

The photosensitive composition of the present invention can be suitably used for color filter substrates, fingerprint sensors, display devices equipped with them, decorative ink materials, and the like.

Claims

A photosensitive composition containing an alkali-soluble resin having a tricyclodecanyl skeleton, a radically polymerizable compound, a photopolymerization initiator, a coloring material and an organic solvent, wherein the alkali-soluble resin having the tricyclodecanyl skeleton occupies The ratio is 20% by mass or more and 40% by mass or less in the solid content, and is contained in the total mass Tg of the solid content excluding the coloring material of the photosensitive composition and the solid content excluding the coloring material of the photosensitive composition A photosensitive composition satisfying a ratio T/M of the number of moles M of carboxyl groups of 1300 or more and 1600 or less.
The weight ratio of units having a tricyclodecanyl skeleton contained in the alkali-soluble resin having a tricyclodecanyl skeleton is 2% by mass or more and 15% by mass or less in the alkali-soluble resin having a tricyclodecanyl skeleton. 2. The photosensitive composition according to 1.
3. The photosensitive composition according to claim 1, wherein the alkali-soluble resin having a tricyclodecanyl skeleton has a weight average molecular weight of 20,000 or more and 40,000 or less.
3. The photosensitive composition according to claim 1, wherein the alkali-soluble resin having a tricyclodecanyl skeleton has a double bond equivalent of 500 or more and 2,000 or less.
1. 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. 3. or the photosensitive composition according to 2.
A color filter substrate having pixels 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 comprising the fingerprint sensor according to claim 7 .