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

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

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Publication number
WO2023021986A1
WO2023021986A1 PCT/JP2022/029742 JP2022029742W WO2023021986A1 WO 2023021986 A1 WO2023021986 A1 WO 2023021986A1 JP 2022029742 W JP2022029742 W JP 2022029742W WO 2023021986 A1 WO2023021986 A1 WO 2023021986A1
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WO
WIPO (PCT)
Prior art keywords
photosensitive composition
mass
alkali
tricyclodecanyl
skeleton
Prior art date
Application number
PCT/JP2022/029742
Other languages
French (fr)
Japanese (ja)
Inventor
小田拓郎
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2022547859A priority Critical patent/JPWO2023021986A1/ja
Priority to CN202280051414.XA priority patent/CN117716293A/en
Priority to KR1020247004142A priority patent/KR20240044426A/en
Publication of WO2023021986A1 publication Critical patent/WO2023021986A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06V—IMAGE OR VIDEO RECOGNITION OR UNDERSTANDING
    • G06V40/00—Recognition of biometric, human-related or animal-related patterns in image or video data
    • G06V40/10—Human or animal bodies, e.g. vehicle occupants or pedestrians; Body parts, e.g. hands
    • G06V40/12—Fingerprints or palmprints
    • G06V40/13—Sensors therefor
    • G06V40/1318—Sensors therefor using electro-optical elements or layers, e.g. electroluminescent sensing

Definitions

  • 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.
  • a photosensitive composition is 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.
  • 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.
  • an alignment mark previously formed on the substrate with a colored composition or the like is used as a reference.
  • 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.
  • 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.
  • 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.
  • 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.
  • the photosensitive composition of the present invention contains an alkali-soluble resin having a tricyclodecanyl skeleton.
  • 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.
  • alkali-soluble resins having a tricyclodecanyl skeleton examples 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.
  • ethylenically unsaturated compounds having a tricyclodecanyl skeleton include, for example, tricyclodecanyl (meth)acrylate and tricyclodecanedimethanol di(meth)acrylate. Copolymers are preferred.
  • 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.
  • 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.
  • 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.
  • the alkali-soluble resin having a tricyclodecanyl skeleton 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.
  • 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 ⁇ -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 ⁇ -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.
  • the alkali-soluble resin having a tricyclodecanyl skeleton preferably has an ethylenically unsaturated group in the side chain.
  • ethylenically unsaturated groups include vinyl groups, allyl groups, acrylic groups, and methacrylic groups.
  • 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.
  • 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.
  • it is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 alky
  • 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.
  • 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.
  • the photosensitive composition of the invention contains a photopolymerization initiator.
  • a photopolymerization initiator refers to a compound that decomposes and/or reacts with light (including ultraviolet rays or electron beams) to generate radicals.
  • 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.
  • 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-benz
  • benzophenone compounds include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone and the like.
  • acetophenone compounds include 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, ⁇ -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
  • 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.
  • imidazole compounds include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.
  • Benzothiazole compounds include, for example, 2-mercaptobenzothiazole.
  • benzoxazole compounds include 2-mercaptobenzoxazole.
  • 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.
  • 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.
  • the photosensitive composition of the invention contains a coloring material.
  • 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.
  • 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.
  • PR C.I. I. Pigment Red
  • 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.
  • yellow colorants include organic pigments, inorganic pigments, and dyes.
  • PY Pigment Yellow
  • 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.
  • green colorants include organic pigments, inorganic pigments, and dyes.
  • 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.
  • PB 15 C.I. I. Pigment Blue
  • PV C.I. I. Pigment Violet
  • PV30 C.I. I. Pigment Violet
  • PV32 C.I. I. Pigment Violet
  • PV37 C.I. I. Pigment Violet
  • PV50 C.I. I. Pigment Violet
  • Dyes include, for example, oil-soluble dyes, acid dyes, direct dyes, basic dyes, and acid mordant dyes.
  • the dye may be made into a lake, or a salt-forming compound of a dye and a nitrogen-containing compound may be used.
  • 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.
  • 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.
  • 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. .
  • 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.
  • the photosensitive composition of the invention contains an organic solvent.
  • 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 monoeth
  • 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.
  • 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.
  • the photosensitive composition of the present invention may contain a dispersant such as a pigment derivative together with the colorant.
  • a dispersant such as a pigment derivative together with the colorant.
  • dispersants include low-molecular-weight dispersants such as pigment intermediates and derivatives, and high-molecular-weight dispersants.
  • 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.
  • polymer dispersants examples 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.
  • 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.
  • 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.
  • 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.
  • 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. .
  • the photosensitive composition of the present invention may contain a chain transfer agent together with the photopolymerization initiator, thereby further improving the sensitivity.
  • 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.
  • 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.
  • a photosensitizer such as a thioxanthone-based sensitizer, an aromatic or aliphatic tertiary amine, and the like.
  • 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.
  • 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.
  • 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.
  • 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-chloropropyltrimeth
  • 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.
  • 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.
  • 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.
  • solid content 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.
  • 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.
  • the number of moles of the carboxyl group is calculated from the number of moles of the acid component.
  • 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.
  • 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.
  • the viscosity change amount ⁇ per solid content change mass ⁇ W when the solid content concentration is changed from 18% by mass to 25% by mass, that is, ⁇ / ⁇ W is 0.50 or more and 0.70 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 ⁇ per solid content change amount ⁇ W can be calculated by the following method.
  • the viscosity change amount ⁇ per solid content change amount ⁇ W is ( ⁇ 1- ⁇ 2)/(W1-W2).
  • Viscosity refers to a value measured with an E-type viscometer at a temperature of 23°C.
  • the viscosity change amount ⁇ per solid content change amount ⁇ W 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. .
  • the viscosity change amount ⁇ per solid content change amount ⁇ W 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. .
  • 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.
  • 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.
  • 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.
  • the color filter substrate of the invention has pixels containing the photocured product of the photosensitive composition of the invention.
  • the fingerprint sensor of the present invention has a photocured product of the photosensitive composition of the present invention.
  • 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
  • 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.
  • 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.
  • 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.
  • the substrate is preferably a film with a thickness of 5 ⁇ m or more, more preferably 10 ⁇ m or more.
  • the substrate is preferably a film having a thickness of 100 ⁇ m or less.
  • Pixels include colored pixels such as red and blue, and transparent pixels.
  • 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.
  • the film thickness of the pixel is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, and even more preferably 1.4 ⁇ m or more. On the other hand, it is preferably 3.0 ⁇ m or less, more preferably 2.8 ⁇ m or less, from the viewpoint of improving the flatness, pattern workability and reliability of the color filter substrate.
  • 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.
  • the film thickness of the black matrix is not particularly specified, it is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m 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.
  • metals such as aluminum, chromium, tantalum, titanium, neodymium or molybdenum, Indium-Tin-Oxide (ITO), Indium-Zinc-Oxide (InZnO), and the like.
  • 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.
  • a spin coater 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.
  • 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.
  • 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.
  • 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.
  • the alkaline developer include 0.02 to 1% by mass of potassium hydroxide or tetramethylammonium hydroxide.
  • 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.
  • 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.
  • 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.
  • TFT thin film transistor
  • TFD thin film diode
  • a liquid crystal display device is completed by attaching a backlight and mounting an IC driver and the like.
  • a 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. .
  • 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 ⁇ m in length, 40 ⁇ m in width, and 1.5 ⁇ m in height. The product was applied so as to cover the pattern so that the film thickness at a location 200 ⁇ m away from the pattern end was 2.5 ⁇ m, 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 ⁇ m, and the closer the slope width L is to 0 ⁇ m, the better the shape retention.
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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 ⁇ m, and the slope width L was 17.3 ⁇ m.
  • the change in line width after 48 hours was less than 1 ⁇ m (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 ⁇ / ⁇ W 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.
  • 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.

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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

感光性組成物、カラーフィルタ基板、指紋センサーおよび表示装置Photosensitive composition, color filter substrate, fingerprint sensor and display device
　本発明は、感光性組成物、カラーフィルタ基板、指紋センサーおよび表示装置に関する。 The present invention relates to a photosensitive composition, a color filter substrate, a fingerprint sensor and a display device.
　液晶表示装置は、軽量、薄型、低消費電力等の特性を活かし、テレビ、ノートパソコン、携帯情報端末、スマートフォン、デジタルカメラ等様々な用途で使用されている。液晶表示装置には、用途に応じて３～６原色の最適な色が要求され、様々な色性能を担うカラーフィルタ基板が使用されている。 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.
　カラーフィルタ基板は、着色画素を形成時に、基板上に感光性組成物をスリットコーターにて塗布、乾燥した後、露光、現像、焼成を行い、作製することが一般的である。カラーフィルタ用の感光性組成物として、種々の感光性組成物が知られている（例えば、特許文献１、特許文献２参照）。これらの感光性組成物は、基板上に塗布された後、フォトリソグラフィー用マスクを用いて露光・現像を行うことで、所望の形状にパターン形成される。 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.
国際公開第２０１７／１６４１２７号WO2017/164127 国際公開第２０１８／１５１０４４号WO2018/151044
　一般に、基板上の感光性組成物の露光を行う際には、基板とフォトリソグラフィー用マスクの位置関係を調整することにより、所望の位置に、所望の形状のパターンを形成することができる。基板とフォトリソグラフィー用マスクの位置関係を調整する際には、予め基板上に着色組成物等で形成したアライメントマークが基準として用いられる。 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.
　しかしながら、アライメントマークを含めた基板上に感光性組成物を塗布した場合、上述した感光性組成物では下地への形状保持性が低いため、基板上方よりカメラを用いてアライメントマークを観察しても、その位置を特定できないという課題があった。 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.
　また、塗布後に感光性組成物を一定時間放置すると、加工特性が大きく変化するといった問題があり、改善が求められていた。 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.
　本発明は、下地基板の凹凸部に対する形状保持性に優れ、また塗布後にて放置しても加工特性の変化が小さい感光性組成物を提供することを目的とする。 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.
　本発明は、トリシクロデカニル骨格を有するアルカリ可溶性樹脂、ラジカル重合性化合物、光重合開始剤、色材および有機溶剤を含有する感光性組成物であって、前記トリシクロデカニル骨格を有するアルカリ可溶性樹脂の占める割合が固形分中２０質量％以上４０質量％以下であり、かつ前記感光性組成物の色材を除く固形分の総質量Ｔｇと前記感光性組成物の固形分中に含まれるカルボキシル基のモル数Ｍの比率Ｔ／Ｍが１３００以上１６００以下を満たす感光性組成物である。 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.
　本発明の感光性組成物によれば、下地基板の凹凸部に対する形状保持性に優れ、また塗布後にて放置しても加工特性の変化が小さい感光性組成物を提供することができる。 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.
実施例記載の形状保持性評価において、パターンを有するガラス基板上に感光性組成物からなる皮膜を形成したときの断面図であり、パターンへの乗り上げ部の高さＨ、傾斜幅Ｌを示す図である。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.
　本発明の感光性組成物は、トリシクロデカニル骨格を有するアルカリ可溶性樹脂、ラジカル重合性化合物、光重合開始剤、色材および有機溶剤を含有する感光性組成物であって、前記トリシクロデカニル骨格を有するアルカリ可溶性樹脂の占める割合が固形分中２０質量％以上４０質量％以下であり、かつ前記感光性組成物の色材を除く固形分の総質量Ｔｇと前記感光性組成物の色材を除く固形分中に含まれるカルボキシル基のモル数Ｍの比率Ｔ／Ｍが１３００以上１６００以下を満たす感光性組成物である。本発明の感光性組成物は、下地基板の凹凸部に対する形状保持性に優れ、また塗布後にて放置しても加工特性の変化を抑制することができる。また、本発明の感光性組成物は形状保持性に優れるため、アライメントマークを含めた基板上に感光性組成物を塗布した場合、アライメントマーク上に形成した皮膜は盛り上がった形状を維持する。そのため、基板上方よりカメラを用いてアライメントマークを観察してもその位置を特定することができる。 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.
　（トリシクロデカニル骨格を有するアルカリ可溶性樹脂）
　本発明の感光性組成物は、トリシクロデカニル骨格を有するアルカリ可溶性樹脂を含有する。トリシクロデカニル骨格を有するアルカリ可溶性樹脂を含有することで、加工性や下地基板の凹凸部に対する形状保持性に優れ、また塗布後にて放置しても加工特性の変化を抑制することができる。 (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.
　トリシクロデカニル骨格を有するアルカリ可溶性樹脂としては、例えば、アクリル樹脂、エポキシ樹脂、ポリイミド樹脂、ウレタン樹脂、尿素樹脂、ポリビニールアルコール樹脂、メラミン樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ポリエステル樹脂、ポリオレフィン樹脂等が挙げられる。これらを２種以上含有してもよい。安定性の面から、アクリル樹脂が好ましく用いられる。 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.
　アクリル樹脂について、トリシクロデカニル骨格を有するエチレン性不飽和化合物としては、例えば、トリシクロデカニル（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレートが挙げられ、不飽和カルボン酸との共重合体が好ましい。 For acrylic resins, ethylenically unsaturated compounds having a tricyclodecanyl skeleton include, for example, tricyclodecanyl (meth)acrylate and tricyclodecanedimethanol di(meth)acrylate. Copolymers are preferred.
　不飽和カルボン酸としては、例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、ビニル酢酸、これらの酸無水物などが挙げられる。これらを２種以上用いてもよい。 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.
　トリシクロデカニル骨格を有するアルカリ可溶性樹脂に含まれるトリシクロデカニル骨格を有するユニットの重量比率は、トリシクロデカニル骨格を有するアルカリ可溶性樹脂中２質量％以上３０質量％以下であることが好ましい。トリシクロデカニル骨格を有するユニットの重量比率は、下地基板の凹凸部に対する形状保持性の観点から、トリシクロデカニル骨格を有するアルカリ可溶性樹脂中３０質量％以下が好ましく、より好ましくは２０質量％以下、さらにより好ましくは１５質量％以下、よりいっそう好ましくは１２質量％以下である。また、塗布後の皮膜の安定性の観点から、トリシクロデカニル骨格を有するアルカリ可溶性樹脂に含まれるトリシクロデカニル骨格を有するユニットの重量比率は、トリシクロデカニル骨格を有するアルカリ可溶性樹脂中１質量％以上が好ましく、より好ましくは２質量％以上、さらにより好ましくは５質量％以上である。また、吐出装置の吐出口閉塞性の観点から、アルカリ可溶性樹脂に含まれるトリシクロデカニル骨格を有するユニットの重量比率は、アルカリ可溶性樹脂中５質量％以上が好ましく、より好ましくは９質量％以上である。 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.
　トリシクロデカニル骨格を有するユニットの重量比率は、トリシクロデカニル骨格を有するアルカリ可溶性樹脂に占める各構成ユニットのモル比率から各構成ユニットの重量を算出することで求めることができる。また、感光性組成物において、トリシクロデカニル骨格を有するアルカリ可溶性樹脂に含まれるトリシクロデカニル骨格を有するユニットの重量比率は、以下の方法により算出することができる。まず、本発明の感光性組成物に含まれる各成分について、分取ＧＰＣ、分取ＨＰＬＣ、カラム精製等の方法により各成分を単離精製し、トリシクロデカニル骨格を有するアルカリ可溶性樹脂の構造を分析して算出することができる。トリシクロデカニル骨格を有するアルカリ可溶性樹脂の構造分析については、具体的には１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＨＭＢＣやＨＭＱＣ等の２次元ＮＭＲ等により同定することができ、構造分析結果から、アルカリ可溶性樹脂全体に占めるトリシクロデカニル骨格の重量比率を計算して、算出することができる。 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.
　トリシクロデカニル骨格を有するアルカリ可溶性樹脂としては、さらに別のエチレン性不飽和化合物を共重合した樹脂でもよい。 The alkali-soluble resin having a tricyclodecanyl skeleton may be a resin obtained by copolymerizing another ethylenically unsaturated compound.
　エチレン性不飽和化合物としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸ｓｅｃ－ブチル、（メタ）アクリル酸イソ－ブチル、（メタ）アクリル酸ｔｅｒｔ－ブチル、（メタ）アクリル酸ｎ－ペンチル、２－ヒドロキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレートなどの不飽和カルボン酸アルキルエステル、スチレン、ｐ－メチルスチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、α－メチルスチレンなどの芳香族ビニル化合物、アミノエチルアクリレートなどの不飽和カルボン酸アミノアルキルエステル、グリシジルアクリレート、グリシジルメタクリレートなどの不飽和カルボン酸グリシジルエステル、酢酸ビニル、プロピオン酸ビニルなどのカルボン酸ビニルエステル、アクリロニトリル、メタクリロニトリル、α－クロルアクリロニトリルなどのシアン化ビニル化合物、１，３－ブタジエン、イソプレンなどの脂肪族共役ジエン、末端に（メタ）アクリロイル基を有するポリスチレン、ポリメチルアクリレート、ポリメチルメタクリレート、ポリブチルアクリレート、ポリブチルメタクリレート、ポリシリコーンなどのマクロモノマーなどが挙げられる。これらを２種以上用いてもよい。 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.
　トリシクロデカニル骨格を有するアルカリ可溶性樹脂は、塗布後の皮膜の安定性の観点から、側鎖にエチレン性不飽和基を有することが好ましい。エチレン性不飽和基としては、例えば、ビニル基、アリル基、アクリル基、メタクリル基などが挙げられる。側鎖にエチレン性不飽和基を有するアクリル樹脂としては、例えば、“サイクロマー”（登録商標）Ｐ（ダイセル化学工業（株））や、アルカリ可溶性カルド樹脂等が挙げられる。 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.
　トリシクロデカニル骨格を有するアルカリ可溶性樹脂の二重結合当量は、塗布後の皮膜の安定性や加工性の観点から、５００以上が好ましく、８００以上がより好ましく、さらに好ましくは１，０００以上である。また、トリシクロデカニル骨格を有するアルカリ可溶性樹脂の二重結合当量は、下地基板の凹凸部に対する形状保持性や加工性や信頼性の観点から、３，０００以下が好ましく、より好ましくは２，０００以下であり、さらに好ましくは１，５００以下である。 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.
　トリシクロデカニル骨格を有するアルカリ可溶性樹脂の重量平均分子量が９，０００以上２００，０００以下であることが好ましい。トリシクロデカニル骨格を有するアルカリ可溶性樹脂の重量平均分子量は、硬化膜の強度の観点から３，０００以上が好ましく、９，０００以上がより好ましい。また、下地基板の凹凸部に対する形状保持性の観点から、１０，０００以上が好ましく、２０，０００以上がより好ましく、３０，０００以上がさらに好ましい。また、感光性組成物の安定性や他成分との相溶性や塗布後の皮膜の安定性の観点から、トリシクロデカニル骨格を有するアルカリ可溶性樹脂の重量平均分子量は２００，０００以下が好ましく、より好ましくは１００，０００以下、さらに好ましくは４０，０００以下である。また、吐出装置の吐出口閉塞性の観点から、トリシクロデカニル骨格を有するアルカリ可溶性樹脂の重量平均分子量は４０，０００以下が好ましく、より好ましくは３５，０００以下である。ここで言うアルカリ可溶性樹脂の重量平均分子量とは、ゲルパーミエーショングロマトグラフィーで測定した標準ポリスチレン換算値を指す。 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.
　本発明の感光性組成物が含有するトリシクロデカニル骨格を有するアルカリ可溶性樹脂の含有量は、固形分中２０質量％以上４０質量％以下である。トリシクロデカニル骨格を有するアルカリ可溶性樹脂の含有量が、固形分中２０質量％より小さいと、下地基板の凹凸部に対する形状保持性が悪化する。トリシクロデカニル骨格を有するアルカリ可溶性樹脂の含有量は、２２質量％以上がより好ましく、２５質量％以上がさらに好ましい。また、トリシクロデカニル骨格を有するアルカリ可溶性樹脂の含有量が、固形分中４０質量％より大きいと、塗布後の皮膜の安定性が悪化する。トリシクロデカニル骨格を有するアルカリ可溶性樹脂の含有量は、固形分中３５質量％以下が好ましく、３０質量％以下がより好ましい。また、吐出装置の吐出口閉塞性の観点から、トリシクロデカニル骨格を有するアルカリ可溶性樹脂の含有量は、固形分中３５質量％以下が好ましく、３２質量％以下がより好ましい。 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.
　（ラジカル重合性化合物）
　本発明の感光性組成物は、ラジカル重合性化合物を含有する。ここで言うラジカル重合性化合物とは、ラジカル重合により反応する化合物を指し、重量平均分子量が１，０００以下の化合物を指す。ラジカル重合性化合物は、不飽和炭化水素基を有する化合物が好ましい。不飽和炭化水素基としては、例えば、（メタ）アクリロイル基、ビニル基、マレイミド基などが挙げられる。これらを２種以上有してもよい。 (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.
　ラジカル重合性化合物としては、例えば、ジペンタエリスリトールペンタ（メタ）アクリレート、テトラトリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタ（メタ）アクリロイルオキシジペンタエリスリトールモノこはく酸エステル、ジペンタエリスリトールヘキサ（メタ）アクリレート等のエチレンオキサイド変性物またはプロピレンオキサイド変性物、スチレン誘導体、多官能マレイミド化合物、ポリ（メタ）アクリレートカルバメート、アジピン酸１，６－ヘキサンジオール（メタ）アクリル酸エステル、無水フタル酸プロピレンオキサイド（メタ）アクリル酸エステル、トリメリット酸ジエチレングリコール（メタ）アクリル酸エステル、ロジン変性エポキシジ（メタ）アクリレート、アルキッド変性（メタ）アクリレートなどのオリゴマー、トリプロピレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート等の２官能（メタ）アクリレート類、トリメチロールプロパントリ（メタ）アクリレート、トリアクリルホルマール、ビスフェノキシエタノールフルオレンジアクリレート、ジシクロペンタンジエニルジアクリレート、これらのアルキル変性物、アルキルエーテル変性物やアルキルエステル変性物などが挙げられる。これらを２種以上含有してもよい。塗布後の皮膜の安定性の観点から、ラジカル重合性化合物として、ペンタエリスリトールトリアクリレートを用いることが好ましい。 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.
　本発明の感光性組成物におけるラジカル重合性化合物の含有量は、パターニング性の観点から、固形分中４０質量％以上が好ましい。一方、製膜時の膜厚ムラを抑制し、焼成時の流動によるパターンの変形を抑制する観点から、ラジカル重合性化合物の含有量は、固形分中、９０質量％以下が好ましく、７０質量％以下がより好ましく、６０質量％以下がさらに好ましい。 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.
　（光重合開始剤）
　本発明の感光性組成物は、光重合開始剤を含有する。光重合開始剤を含有することで、パターニング時の感度を向上させることができる。ここで、光重合開始剤とは、光（紫外線または電子線を含む）により分解および／または反応し、ラジカルを発生させる化合物を指す。光重合開始剤としては、例えば、オキシムエステル系化合物、ベンゾフェノン系化合物、アセトフェノン系化合物、オキサントン系化合物、アントラキノン系化合物、イミダゾール系化合物、ベンゾチアゾール系化合物、ベンゾオキサゾール系化合物、カルバゾール系化合物、トリアジン系化合物、リン系化合物、チタノセン系化合物などが挙げられる。 (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.
　より具体的には、オキシムエステル化合物としては、例えば、１，２－オクタンジオン，１－〔４－（フェニルチオ）フェニル〕－，２－（Ｏ－ベンゾイルオキシム）、エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム）、エタノン，１－〔９－エチル－６－（２－メチル－４－テトラヒドロフラニルメトキシベンゾイル）－９Ｈ－カルバゾール－３－イル〕－，１－（Ｏ－アセチルオキシム）、エタノン，１－〔９－エチル－６－｛２－メチル－４－（２，２－ジメチル－１，３－ジオキソラニル）メトキシベンゾイル｝－９Ｈ－カルバゾール－３－イル〕－，１－（Ｏ－アセチルオキシム）、１，２－オクタンジオン，１－［４－（フェニルチオ）－２－（Ｏ－ベンゾイルオキシム）］、“アデカアークルズ”（商標登録）Ｎ－１９１９、ＮＣＩ－９３０（（株）ＡＤＥＫＡ製）、“ＩＲＧＡＣＵＲＥ”（商標登録）ＯＸＥ０１、ＯＸＥ０２（ＢＡＳＦ（株）製）などが挙げられる。ベンゾフェノン系化合物としては、例えば、ベンゾフェノン、Ｎ，Ｎ’－テトラエチル－４，４’－ジアミノベンゾフェノン、４－メトキシ－４’－ジメチルアミノベンゾフェノンなどが挙げられる。アセトフェノン系化合物としては、例えば、２，２－ジエトキシアセトフェノン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタール、α－ヒドロキシイソブチルフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－１－プロパン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、“ＩＲＧＡＣＵＲＥ”（商標登録）３６９、３７９、９０７（ＢＡＳＦ（株）製）などが挙げられる。アントラキノン系化合物としては、例えば、ｔ－ブチルアントラキノン、１－クロロアントラキノン、２，３－ジクロロアントラキノン、３－クロル－２－メチルアントラキノン、２－エチルアントラキノン、１，４－ナフトキノン、９，１０－フェナントラキノン、１，２－ベンゾアントラキノン、１，４－ジメチルアントラキノン、２－フェニルアントラキノンなどが挙げられる。イミダゾール系化合物としては、例えば、２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール２量体などが挙げられる。ベンゾチアゾール系化合物としては、例えば、２－メルカプトベンゾチアゾールなどが挙げられる。ベンゾオキサゾール系化合物としては、例えば、２－メルカプトベンゾオキサゾールなどが挙げられる。トリアジン系化合物としては、例えば、４－（ｐ－メトキシフェニル）－２，６－ジ－（トリクロロメチル）－ｓ－トリアジンなどが挙げられる。これらを２種以上含有してもよい。 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.
　光重合開始剤の含有量は、感度、パターニング性、加工性の観点から、感光性組成物の色材を除く固形分中、１質量％以上が好ましく、２質量％以上がより好ましく、５質量％以上がさらに好ましい。一方、光重合開始剤の含有量は、感度、パターニング性、加工性、耐熱性の観点から、感光性組成物の色材を除く固形分中、３０質量％以下が好ましく、２０質量％以下がより好ましく、１５質量％以下がさらに好ましい。 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.
　（色材）
　本発明の感光性組成物は、色材を含有する。色材としては、有機顔料、無機顔料、染料等が挙げられ、これらを２種以上含有してもよい。これらの中でも、透過率をより向上させる観点から、有機顔料、染料が好ましい。 (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.
　赤色色材としては、例えば、Ｃ．Ｉ．ピグメントレッド（以下、「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、臭素基を有するジケトピロロピロール色材などが挙げられる。画素の輝度特性の観点から、ＰＲ２５４やＰＲ１７７、臭素基を有するジケトピロロピロール色材が好ましく、明るさ、鮮やかさ、混色防止の観点から、臭素基を有するジケトピロロピロール色材を用いることが好ましい。 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.
　黄色色材としては、有機顔料、無機顔料、染料などが挙げられ、例えば、Ｃ．Ｉ．ピグメントイエロー（以下、「ＰＹ」）１２、ＰＹ１３、ＰＹ１７、ＰＹ２０、ＰＹ２４、ＰＹ８３、ＰＹ８６、ＰＹ９３、ＰＹ９５、ＰＹ１０９、ＰＹ１１０、ＰＹ１１７、ＰＹ１２５、ＰＹ１２９、ＰＹ１３７、ＰＹ１３９、ＰＹ１４７、ＰＹ１４８、ＰＹ１５０、ＰＹ１５３、ＰＹ１５４、ＰＹ１６６、ＰＹ１６８（以上、番号はいずれもカラーインデックスＮｏ．）などが挙げられる。これらを２種以上含有してもよい。色純度、光透過率およびコントラストの観点から、ＰＹ１２９、ＰＹ１３９、ＰＹ１５０、ＰＹ１８５が好ましく、ＰＹ１５０、ＰＹ１８５がより好ましい。 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.
　緑色色材としては、有機顔料、無機顔料、染料などが挙げられ、例えば、Ｃ．Ｉ．ピグメントグリーン（以下、「ＰＧ」）ＰＧ１、ＰＧ２、ＰＧ４、ＰＧ７、ＰＧ８、ＰＧ１０、ＰＧ１３、ＰＧ１４、ＰＧ１５、ＰＧ１７、ＰＧ１８、ＰＧ１９、ＰＧ２６、ＰＧ３６、ＰＧ３８、ＰＧ３９、ＰＧ４５、ＰＧ４８、ＰＧ５０、ＰＧ５１、ＰＧ５４、ＰＧ５５、ＰＧ５８、ＰＧ５９（以上、番号はいずれもカラーインデックスＮｏ．）などが挙げられる。これらを２種以上含有してもよい。 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.
　オレンジ色色材としては、例えば、Ｃ．Ｉ．ピグメントオレンジ（以下、「ＰＯ」）１３、ＰＯ３１、ＰＯ３６、ＰＯ３８、ＰＯ４０、ＰＯ４２、ＰＯ４３、ＰＯ５１、ＰＯ５５、ＰＯ５９、ＰＯ６１、ＰＯ６４、ＰＯ６５、ＰＯ７１などが挙げられる。 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.
　青色色材としては、例えば、Ｃ．Ｉ．ピグメントブルー（以下、「ＰＢ」）１５、ＰＢ１５：３、ＰＢ１５：４、ＰＢ１５：６、ＰＢ２１、ＰＢ２２、ＰＢ６０、ＰＢ６４などが挙げられる。 For example, C.I. I. Pigment Blue (hereinafter "PB") 15, PB15:3, PB15:4, PB15:6, PB21, PB22, PB60, PB64 and the like.
　紫色色材としては、例えば、Ｃ．Ｉ．ピグメントバイオレット（以下「ＰＶ」）１９、ＰＶ２３、ＰＶ２９、ＰＶ３０、ＰＶ３２、ＰＶ３７、ＰＶ４０、ＰＶ５０などが挙げられる（以上、番号はいずれもカラーインデックスＮｏ．）。 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).
　染料としては、例えば、油溶性染料、酸性染料、直接染料、塩基性染料、酸性媒染染料などが挙げられる。また、上記染料をレーキ化したり、染料と含窒素化合物との造塩化合物としても構わない。 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.
　赤色、緑色、青色、紫色または黄色の染料としては、例えば、直接染料、酸性染料、塩基性染料などが挙げられる。これら染料の具体例としては、例えば、アゾ系染料、ベンゾキノン系染料、ナフトキノン系染料、アントラキノン系染料、キサンテン系染料、シアニン系染料、スクアリリウム系染料、クロコニウム系染料、メロシアニン系染料、スチルベン系染料、ジアリールメタン系染料、トリアリールメタン系染料、フルオラン系染料、スピロピラン系染料、フタロシアニン系染料、インジゴ系染料、フルギド系染料、ニッケル錯体系染料、アズレン系染料などが挙げられる。染料は感光性組成物中に溶解させても、粒子として分散させても構わない。 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.
　熱、光、酸、アルカリまたは有機溶剤等に対する耐性を高めるため、塩基性染料としては、有機スルホン酸や有機カルボン酸等の有機酸または過塩素酸とからなる造塩化合物が好ましく、トビアス酸等のナフタレンスルホン酸または過塩素酸とからなる造塩化合物がより好ましい。同様に、熱、光、酸、アルカリまたは有機溶剤等に対する耐性を高めるため、酸性染料および直接染料としては、四級アンモニウム塩、一～三級アミンまたはスルホンアミドとからなる造塩化合物が好ましい。 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.
　色材の含有量は、塗布装置の吐出部の閉塞の観点から、感光性組成物の固形分中、１０質量％以上が好ましく、より好ましくは２０質量％以上である。また、色材の含有量は、皮膜の安定性の観点から、感光性組成物の固形分中、４０質量％以下が好ましく、より好ましくは３５質量％以下、さらにより好ましくは３０質量％以下である。 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.
　感光性組成物に含まれる色材は、レーザーラマン分光法（Ａｒ＋レーザー（４５７．９ｎｍ））や、ＭＡＬＤＩ質量分析装置または飛行時間型二次イオン質量分析計による質量分析により、同定することができる。 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. .
　また、感光性組成物中における色材の含有量は、ＭＡＬＤＩ質量分析装置または飛行時間型二次イオン質量分析計による質量分析により定量することができ、得られた色材の質量と、他の成分の含有量から、感光性組成物中の固形分中に占める割合（質量％）を求めることができる。なお、感光性組成物の原料の配合比が既知の場合には、色材の配合量と、他の成分の配合量から、感光性組成物中の固形分中に占める割合（質量％）を求めることができる。 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.
　（有機溶剤）
　本発明の感光性組成物は、有機溶剤を含有する。有機溶剤としては、例えば、ジエチレングリコールモノブチルエーテルアセテート、ベンジルアセテート、エチルベンゾエート、メチルベンゾエート、マロン酸ジエチル、２－エチルヘキシルアセテート、２－ブトキシエチルアセテート、エチレングリコールモノブチルエーテルアセテート、シュウ酸ジエチル、アセト酢酸エチル、シクロヘキシルアセテート、３－メトキシ－ブチルアセテート、アセト酢酸メチル、エチル－３－エトキシプロピオネート、２－エチルブチルアセテート、イソペンチルプロピオネート、プロピレングリコールモノメチルエーテルプロピオネート、酢酸ペンチル、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、モノエチルエーテル、メチルカルビトール、エチルカルビトール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールターシャリーブチルエーテル、ジプロピレングリコールモノメチルエーテル、酢酸エチル、酢酸ブチル、酢酸イソペンチルブタノール、３－メチル－２－ブタノール、３－メチル－３－メトキシブタノール、シクロペンタノン、シクロヘキサノン、キシレン、エチルベンゼン、ソルベントナフサなどが挙げられる。これらを２種以上含有してもよい。 (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.
　本発明の感光性組成物が含有する有機溶剤の成分の中で、沸点が１５０℃以下である有機溶剤の割合が８０質量％以上であることが、下地基板の凹凸部に対する形状保持性の観点から好ましい。 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
　（その他の成分）
　本発明の感光性組成物は、さらに、分散剤、連鎖移動剤、光増感剤、重合禁止剤、密着改良剤、界面活性剤、架橋剤などを含有してもよい。 (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.
　（分散剤）
　本発明の感光性組成物は、色材とともに、顔料誘導体などの分散剤を含有してもよい。分散剤としては、例えば、顔料の中間体や誘導体等の低分子分散剤、高分子分散剤などが挙げられる。顔料誘導体としては、例えば、顔料の適度な湿潤や安定化に資する、顔料骨格のアルキルアミン変性体、カルボン酸誘導体、スルホン酸誘導体などが挙げられる。微細顔料の安定化に顕著な効果を有する、顔料骨格のスルホン酸誘導体が好ましい。 (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.
　高分子分散剤としては、例えば、ポリエステル、ポリアルキルアミン、ポリアリルアミン、ポリイミン、ポリアミド、ポリウレタン、ポリアクリレート、ポリイミド、ポリアミドイミドやこれらの共重合体などが挙げられる。これらを２種以上含有してもよい。これら高分子分散剤の中でも、固形分換算のアミン価が５～２００ｍｇＫＯＨ／ｇであり酸価が１～１００ｍｇＫＯＨ／ｇであるものが好ましい。中でも、塩基性基を有する高分子分散剤が好ましく、顔料分散液および感光性組成物の保存安定性を向上させることができる。塩基性基を有する、市販品の高分子分散剤としては、例えば、“ソルスパース”（登録商標）（アビシア社製）、“ＥＦＫＡ”（登録商標）（エフカ社製）、“アジスパー”（登録商標）（味の素ファインテクノ（株）製）、“ＢＹＫ”（登録商標）（ビックケミー社製）が挙げられる。これらを２種以上含有してもよい。中でも“ソルスパース”（登録商標）２４０００（アビシア社製）、“ＥＦＫＡ”（登録商標）４３００、４３３０（エフカ社製）、４３４０（エフカ社製）、“アジスパー”（登録商標）ＰＢ８２１、ＰＢ８２２（味の素ファインテクノ（株）製）、“ＢＹＫ”（登録商標）１６１～１６３、２０００、２００１、６９１９、２１１１６（ビックケミー社製）が好ましい。 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.
　本発明の感光性組成物が高分子分散剤を含有する場合、高分子分散剤とアルカリ可溶性樹脂の合計の含有量は、製膜時の膜厚ムラを抑制する観点から、固形分中１０質量％以上が好ましく、２０質量％以上がより好ましく、３０質量％以上がさらに好ましい。一方、パターニング性の観点から、高分子分散剤とアルカリ可溶性樹脂の合計の含有量は、感光性組成物の色材を除く固形分中、６０質量％以下が好ましく、５０質量％以下がより好ましい。 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. .
　（連鎖移動剤）
　本発明の感光性組成物は、光重合開始剤と合わせて連鎖移動剤を含有してもよく、感度をより向上させることができる。連鎖移動剤としては、例えば、チオグリコール酸、チオリンゴ酸、チオサリチル酸、２－メルカプトプロピオン酸、３－メルカプトプロピオン酸、３－メルカプト酪酸、Ｎ－（２－メルカプトプロピオニル）グリシン、２－メルカプトニコチン酸、３－［Ｎ－（２－メルカプトエチル）カルバモイル］プロピオン酸、３－［Ｎ－（２－メルカプトエチル）アミノ］プロピオン酸、Ｎ－（３－メルカプトプロピオニル）アラニン、２－メルカプトエタンスルホン酸、３－メルカプトプロパンスルホン酸、４－メルカプトブタンスルホン酸、ドデシル（４－メチルチオ）フェニルエーテル、２－メルカプトエタノール、３－メルカプト－１，２－プロパンジオール、１－メルカプト－２－プロパノール、３－メルカプト－２－ブタノール、メルカプトフェノール、２－メルカプトエチルアミン、２－メルカプトイミダゾール、２－メルカプト－３－ピリジノール、２－メルカプトベンゾチアゾール、メルカプト酢酸、トリメチロールプロパントリス（３－メルカプトプロピオネート）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、“カレンズ”（登録商標）ＭＴ　ＰＥ－１（昭和電工（株）製）、“カレンズ”（登録商標）ＭＴ　ＮＲ－１（昭和電工（株）製）、“カレンズ”（登録商標）ＭＴ　ＢＤ－１（昭和電工（株）製）、等のメルカプト化合物、該メルカプト化合物を酸化して得られるジスルフィド化合物、ヨード酢酸、ヨードプロピオン酸、２－ヨードエタノール、２－ヨードエタンスルホン酸、３－ヨードプロパンスルホン酸等のヨード化アルキル化合物が挙げられる。これらを２種以上含有してもよい。 (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.
　（光増感剤）
　本発明の感光性組成物は、さらに光増感剤を含有してもよく、光増感剤としては、チオキサントン系増感剤、芳香族または脂肪族の第３級アミンなどが挙げられる。チオキサントン系増感剤としては、例えば、チオキサントン、２－クロロチオキサントン、２，４－ジエチルチオキサンテン－９－オン、“ＫＡＹＡＣＵＲＥ”（登録商標）ＤＥＴＸ－Ｓ（日本化薬（株）製）等が挙げられる。これらを２種以上含有してもよい。 (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.
　（重合禁止剤）
　本発明の感光性組成物は、さらに重合禁止剤を含有してもよく、安定性を向上させることができる。重合禁止剤は、一般的に、熱、光、ラジカル開始剤などによって発生したラジカルによる重合を禁止または停止する作用を示し、一般的には、熱硬化性樹脂のゲル化防止やポリマー製造時の重合停止などに使用される。重合禁止剤としては、例えば、ヒドロキノン、ｔｅｒｔ－ブチルヒドロキノン、２，５－ビス（１，１，３，３－テトラメチルブチル）ヒドロキノン、２，５－ビス（１，１－ジメチルブチル）ヒドロキノン、カテコール、ｔｅｒｔ－ブチルカテコールなどが挙げられる。これらを２種以上含有してもよい。安定性と感光特性のバランスの観点から、重合禁止剤の含有量は、固形分中０．０００１質量％以上が好ましく、０．００５質量％以上がより好ましい。また、安定性と感光特性のバランスの観点から、重合禁止剤の含有量は、固形分中１質量％以下が好ましく、０．５質量％以下がより好ましい。 (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.
　（密着改良剤）
　本発明の感光性組成物は、さらに密着改良剤を含有してもよく、感光性組成物の塗膜の基板への密着性を向上させることができる。密着改良剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２－メトキシエトキシ）シラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－クロロプロピルメチルジメトキシシラン、３－クロロプロピルトリメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシランなどのシランカップリング剤が挙げられる。これらを２種以上含有してもよい。 (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.
　（界面活性剤）
　本発明の感光性組成物は、さらに界面活性剤を含有してもよく、感光性組成物の塗布性および塗膜表面の均一性を向上させることができる。界面活性剤としては、例えば、ラウリル硫酸アンモニウム、ポリオキシエチレンアルキルエーテル硫酸トリエタノールアミンなどの陰イオン界面活性剤、ステアリルアミンアセテート、ラウリルトリメチルアンモニウムクロライドなどの陽イオン界面活性剤、ラウリルジメチルアミンオキサイド、ラウリルカルボキシメチルヒドロキシエチルイミダゾリウムベタインなどの両性界面活性剤、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ソルビタンモノステアレートなどの非イオン界面活性剤、フッ素系界面活性剤やシリコン系界面活性剤などが挙げられる。これらを２種以上含有してもよい。界面活性剤の含有量は、塗膜の面内均一性の観点から、感光性組成物中０．００１～１０質量％が好ましい。 (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.
　（感光性組成物）
　本発明の感光性組成物において、感光性組成物の色材を除く固形分の総質量Ｔ（グラム）と前記感光性組成物の色材を除く固形分中に含まれるカルボキシル基のモル数Ｍの比率Ｔ／Ｍが、１３００以上１６００以下を満たすことが、塗布後の皮膜の安定性や加工性、下地基板の凹凸部に対する形状保持性の観点から重要である。形状保持性に優れることで、マーク部の表示読み取りが良好になる。ここで言う固形分とは、感光性組成物に含まれる成分の中で、有機溶剤を除く全成分のことを指す。 (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.
　感光性組成物の色材を除く固形分中に含まれるカルボキシル基のモル数Ｍは、配合する各原料のカルボン酸量から算出することができ、具体的には以下の方法により測定することができる。まず、感光性組成物を計量し、その中に含まれる電位差自動測定装置等により酸成分のモル数を測定し、感光性組成物の色材を除く固形分中に含まれる酸成分のモル数を求めることができる。中和に要する酸成分については、分取ＧＰＣ、分取ＨＰＬＣ、カラム精製等の方法により各成分を単離精製し、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＨＭＢＣやＨＭＱＣ等の２次元ＮＭＲ、ＩＲ等により同定することができ、酸成分のモル数の中で、カルボキシル基のモル数を算出する。ここで、有機溶媒等の固形分に含まれない成分に酸成分が存在する場合は、それらの酸成分のモル数を差し引いて、感光性組成物の色材を除く固形分中に含まれるカルボキシル基のモル数Ｍを算出することができる。 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.
　Ｔ／Ｍが１３００より小さいと、塗布後の皮膜の安定性が悪化する。Ｔ／Ｍは１３２０以上が好ましく、より好ましくは１３５０以上、さらに好ましくは１４００以上である。また、Ｔ／Ｍが１６００より大きいと、下地基板の凹凸部に対する形状保持性が悪化する。Ｔ／Ｍは１５９０以下が好ましく、より好ましくは１５８０以下、さらに好ましくは１５５０以下、さらにより好ましくは１５００以下である。 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.
　本発明の感光性組成物において、固形分濃度を１８質量％から２５質量％に変化させたときの固形分変化質量ΔＷ当たりの粘度変化量Δη、すなわちΔη／ΔＷが０．５０以上０．７０以下であることが、下地基板の凹凸部に対する形状保持性や吐出装置の吐出口閉塞性の観点から好ましい。ここで言う、固形分変化量ΔＷ当たりの粘度変化量Δηは、以下の方法により計算できる。まず感光性組成物の固形分組成が同じで、混合もしくは単一の有機溶剤の配合比率のみが異なる２種類の感光性組成物Ｓ１、Ｓ２を準備し、その固形分濃度がそれぞれＷ１、Ｗ２（単位は質量％。ただし、Ｗ１＞Ｗ２）、その粘度がそれぞれη１、η２（単位はｃＰ）であるとする。この場合の固形分変化量ΔＷ当たりの粘度変化量Δηは、（η１－η２）／（Ｗ１－Ｗ２）となる。粘度は温度２３℃におけるＥ型粘度計での測定値のことを指す。固形分変化量ΔＷ当たりの粘度変化量Δηは、下地基板の凹凸部に対する形状保持性の観点から、０．５０以上が好ましく、より好ましくは０．５３以上、さらに好ましくは０．５６以上である。また、固形分変化量ΔＷ当たりの粘度変化量Δηは、吐出装置の吐出口閉塞性の観点から、０．７０以下が好ましく、より好ましくは０．６４以下、さらに好ましくは０．６０以下である。 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. .
　（感光性組成物の製造方法）
　本発明の感光性樹脂組成物の製造方法は、とくに制限はなく、汎用の方法で製造することができる。例えば、フラスコや反応窯のような容器内に、前記トリシクロデカニル骨格を有するアルカリ可溶性樹脂、前記ラジカル重合性化合物、光重合開始剤、色材を含む分散液、必要によりその他の前記添加剤、および有機溶剤を添加し、撹拌することで、得ることができる。このとき、各成分を有機溶剤で希釈した溶液、有機溶剤で溶解した溶解溶液を用いてもよい。各成分を添加する順番はいずれでもよく、また、得られた感光性組成物をろ過してもよい。 (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.
　（カラーフィルタ基板、指紋センサー）
　次に、本発明のカラーフィルタ基板や指紋センサーについて説明する。本発明のカラーフィルタ基板は、本発明の感光性組成物の光硬化物を含む画素を有する。また、本発明の指紋センサーは、本発明の感光性組成物の光硬化物を有する。さらに、本発明のカラーフィルタ基板や指紋センサーに、ブラックマトリックス、フォトスペーサー、オーバーコート層、配向膜、偏光板、位相差板、反射防止膜、透明電極、拡散板等を有してもよい。 (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.
　本発明のカラーフィルタ基板や指紋センサーに用いられる基板としては、例えば、ソーダガラス、無アルカリガラス、ホウケイ酸ガラス、石英ガラス、アルミノホウケイ酸ガラス、アルミノケイ酸塩ガラス、アルカリアルミノケイ酸塩ガラス、表面をシリカコートしたソーダライムガラス等の無機ガラスの板や、シリコンウェハ、有機プラスチックのフィルムやシート等が挙げられる。これらを２種以上積層してもよい。なお、本発明のカラーフィルタ基板を備える表示装置が、反射型の表示装置である場合やシリコンＯＬＥＤのように発光素子を有する表示装置である場合は、基板は不透明であっても構わない。 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.
　有機プラスチックのフィルムやシートは、自立膜であってもよいし、例えばガラス基板などの基板上に塗布等により形成された膜であってもよい。かかる塗布膜の場合、レーザー等により基板と膜との密着力を適度に調整して剥離することができる。有機プラスチックの材質としては、例えば、ポリプロピレン、ポリエチレン、ポリスチレン、ポリエチレンテレフタレート（ＰＥＴ）などのポリエステル、ポリフェニレンサルファイド（ＰＰＳ）、ポリイミド、ポリアミド、ポリアミドイミド、ポリエーテルスルホン、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素含有ポリマー、ポリエーテルエーテルケトン、ポリフェニレンエーテル、ポリアリレート、ポリスルホンなどが挙げられる。 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.
　基板の強度の観点から、基板は厚さ５μｍ以上のフィルムが好ましく、１０μｍ以上がより好ましい。一方、柔軟性の観点から、基板は厚さ１００μｍ以下のフィルムが好ましい。 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.
　画素としては、赤や青等の着色画素と透明画素が挙げられる。画素を構成する材料としては、例えば、本発明の感光性組成物や、アクリル樹脂やポリイミド樹脂等のバインダー樹脂とラジカル重合性化合物を含有する着色感光性組成物などが挙げられる。画素の膜厚は、色純度を向上させる観点から、０．５μｍ以上が好ましく、１．０μｍ以上がより好ましく、１．４μｍ以上がさらに好ましい。一方、カラーフィルタ基板の平坦性、パターン加工性および信頼性を向上させる観点から、３．０μｍ以下が好ましく、２．８μｍ以下がより好ましい。また、指紋センサーの読み取り性能を高めるために、サイズの大きな着色部材を、本発明の感光性組成物からなる部材で形成することができる。 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.
　ブラックマトリックスは、画素間の光漏れによるコントラストや色純度の低下を防止するものであり、画素間や額縁部に配置されることが好ましい。ブラックマトリックスを構成する材料としては、例えば、アクリル樹脂やポリイミド樹脂等のバインダー樹脂とラジカル重合性化合物を含有する感光性組成物、黒色に着色された非感光性樹脂組成物などが挙げられる。ブラックマトリックスの膜厚に特に指定はないが、遮光性の観点から、０．５μｍ以上が好ましく、１．０μｍ以上がより好ましい。 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.
　カラーフィルタ基板に形成するフォトスペーサーは、対向する基板との間に一定のギャップを設けるものであり、ギャップ間に液晶化合物などを充填することができる。そのため、液晶表示装置の製造に際してスペーサーを配置する工程を省略することができる。フォトスペーサーは、カラーフィルタ基板の特定の場所に、液晶表示装置を作製した際に対向基板と接するように固定されてなることが好ましい。フォトスペーサーを構成する材料としては、例えば、アクリル樹脂やポリイミド樹脂等のバインダー樹脂とラジカル重合性化合物を含有する感光性組成物などが挙げられる。フォトスペーサーの形状としては、例えば、円柱状、角柱状、円錐台形状、角錐台形状等が挙げられる。フォトスペーサーの径や高さは、特に指定はなく、いずれのものを用いてもよい。 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.
　オーバーコート層は、カラーフィルタ基板の画素からの不純物の透過を抑制したり、カラーフィルタ基板の画素による段差を平坦化させるものである。オーバーコート層を構成する材料としては、例えば、エポキシ樹脂、アクリルエポキシ樹脂、アクリル樹脂、シロキサン樹脂、ポリイミド樹脂、平坦化材料として市販されている感光性または非感光性の材料などが挙げられる。 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.
　透明電極を構成する材料としては、例えば、アルミ、クロム、タンタル、チタン、ネオジム若しくはモリブデン等の金属、Ｉｎｄｉｕｍ－Ｔｉｎ－Ｏｘｉｄｅ（ＩＴＯ）、Ｉｎｄｉｕｍ－Ｚｉｎｃ－Ｏｘｉｄｅ（ＩｎＺｎＯ）等が挙げられる。 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.
　（カラーフィルタ基板、指紋センサーの製造方法）
　カラーフィルタ基板や指紋センサーの製造方法としては、例えば、基板上に、樹脂組成物からなる画素をパターン形成する方法が挙げられる。以下に、本発明の感光性組成物からなる画素を有するカラーフィルタ基板を例に製造方法を説明する。基板上に、本発明の感光性組成物を塗布し、フォトマスクを用いた選択的な露光および現像によりパターン化し、焼成することにより画素等の部材を形成し、カラーフィルタ基板を得ることができる。 (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. .
　本発明の感光性組成物を基板上に塗布する方法としては、例えば、スピンコーター、バーコーター、ブレードコーター、ロールコーター、ダイコーター、インクジェット印刷法、スクリーン印刷法、基板を感光性組成物中に浸漬する方法、感光性組成物を基板に噴霧する方法などが挙げられる。 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.
　続いて、感光性組成物を塗布した基板を乾燥することにより、基板上に感光性組成物の塗布膜を形成する。乾燥方法としては、例えば、風乾、加熱乾燥、真空乾燥などが挙げられる。これらを２種以上組み合わせてもよく、例えば、減圧乾燥を行った後、加熱乾燥することが好ましい。加熱乾燥の温度は８０～１３０℃が好ましく、加熱乾燥装置としては熱風オーブン、ホットプレートが好ましい。なお、ブラックマトリックスを有するカラーフィルタ基板の場合、予めブラックマトリックスを形成した基板上に、感光性組成物の塗布膜を形成することが好ましい。 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.
　次に、感光性組成物の塗布膜上にフォトマスクを配置し、選択的に露光を行う。露光機としては、例えば、プロキシミティ露光機、ミラープロジャクション露光機、レンズスキャン露光機、ステッパー等が挙げられる。精度の観点から、レンズスキャン露光機が好ましい。また、露光に用いる光源としては、例えば、超高圧水銀灯、ケミカル灯、高圧水銀灯等が挙げられる。 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.
　その後、アルカリ性現像液による現像により未露光部を除去し、塗布膜パターンを形成する。アルカリ性現像液に用いるアルカリ性物質としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア水等の無機アルカリ類、エチルアミン、ｎ－プロピルアミン等の１級アミン類、ジエチルアミン、ジ－ｎ－プロピルアミン等の２級アミン類、トリエチルアミン、メチルジエチルアミン等の３級アミン類、テトラメチルアンモニウムヒドロキシド等の有機アルカリ類等が挙げられる。アルカリ性現像液としては、例えば、０．０２～１質量％の水酸化カリウムまたはテトラメチルアンモニウムヒドロキシド等が挙げられる。 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.
　その後、得られた塗布膜パターンを加熱処理することにより、画素がパターニングされたカラーフィルタ基板を得る。加熱処理は、空気中、窒素雰囲気中、真空中のいずれで行ってもよい。加熱温度は８０～２５０℃が好ましい。加熱時間は５分間～５時間が好ましい。加熱処理装置としては、熱風オーブン、ホットプレートが好ましい。加熱処理は連続的に行っても段階的に行ってもよい。 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.
　カラーフィルタ基板が有する３～６色の各画素について、上記方法により順次画素形成を行う。各色の形成順序は特に限定されないが、染料を含む画素を形成する場合、色材の色移りをより抑制する観点から、染料を含む画素を、他の画素形成の後に形成することが好ましい。 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.
　（表示装置）
　本発明のカラーフィルタ基板は、液晶ディスプレイ、有機ＥＬディスプレイ、電子ペーパー等の表示装置の構成要素とすることができ、画像表示装置として使用できる。すなわち、本発明の表示装置は、本発明のカラーフィルタ基板を有する。さらに、表示装置には、外部光源等の光源や輝度向上フィルムや拡散板等の各種フィルム等を有してもよい。表示装置とは、画面の一部を視認させて、画像を表示する装置のことを指す。表示装置としては、例えば、透過型液晶ディスプレイ、半透過型液晶ディスプレイ、反射型液晶ディスプレイ、有機ＥＬディスプレイ、無機ＥＬディスプレイ、量子ドットディスプレイ、電子ペーパー等が挙げられる。反射型表示装置としては、ウエアラブル端末、電子看板、デジタルサイネージ、電子棚札などの、屋外光や室内光で表示する装置が挙げられる。 (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.
　本発明の表示装置は、本発明の感光性組成物の光硬化物を有する指紋センサーを有する表示装置である。ここで言う、指紋センサーを有する表示装置とは、画像表示装置の画像表示面に指紋センサーが設置され、画像表示部分に指を置くことで、指紋を検出する機能を有する表示装置である。指紋センサーとしては、公知の指紋センサーを使用することができる。画像表示装置に複数の認証センサーを配置することにより、指紋を検出する位置が、特定の位置に限定されず、画像表示部分の複数の位置での指紋の検出が可能になる。 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.
　（表示装置の製造方法）
　本発明の表示装置の製造方法の一例として、カラーフィルタ基板を有する液晶表示装置の製造方法を以下に示す。本発明のカラーフィルタ基板とアレイ基板とを、それらの基板上に設けられた液晶配向膜およびセルギャップ保持のためのスペーサーを介して、対向させて貼り合わせる。なお、アレイ基板上に薄膜トランジスタ（ＴＦＴ）素子若しくは薄膜ダイオード（ＴＦＤ）素子、走査線または信号線等を設けることで、ＴＦＴ液晶表示装置またはＴＦＤ液晶表示装置を製造することができる。次に、シール部に設けられた注入口から液晶を注入した後に、注入口を封止する。さらに、バックライトを取り付け、ＩＣドライバー等を実装することにより、液晶表示装置が完成する。なお、バックライトとしては、２波長ＬＥＤ、３波長ＬＥＤまたはＣＣＦＬ等を用いることができるが、液晶表示装置の色再現範囲が拡大でき、かつ消費電力を低く押さえられることから、３波長ＬＥＤが好ましい。 (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. .
　以下に実施例を挙げて本発明を説明するが、本発明はこれらの実施例に限定されるものではない。まず、実施例および比較例における評価方法について説明する。また各実施例、比較例で用いた他の成分は、下記のとおりである。 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.
　ラジカル重合性化合物
Ｃ１：ペンタエリスリトールトリアクリレート（構造中にカルボキシル基を有しない。）
　光重合開始剤
Ｄ１：“アデカアークルズ”（登録商標）ＮＣＩ８３１（ＡＤＥＫＡ（株）製、構造中にカルボキシル基を有しない。）
　有機溶剤
Ｅ１：プロピレングリコールモノメチルエーテルアセテート。 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.
　＜形状保持性評価＞
　図１に示す通り、縦４００μｍ、横４０μｍ、高さ１．５μｍの着色組成物からなるパターン形状を有するガラス基板上に、実施例１～７および比較例１～４により得られた感光性組成物を、パターン端部から２００μｍ離れた箇所の膜厚が２．５μｍになるよう、パターンを覆うように塗布し、９０℃で１０分間乾燥させ、感光性組成物からなる皮膜を形成した。パターンへの乗り上げ部の高さＨ、傾斜幅Ｌを（株）キーエンス製レーザー顕微鏡ＶＫ－９７１０にて計測し、形状保持性を評価した。高さＨが２．５μｍに近いほど、また傾斜幅Ｌが０μｍに近いほど、形状保持性に優れていることを示す。 <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.
　＜皮膜安定性評価＞
　実施例１～７および比較例１～４により得られた感光性組成物をガラス基板上に塗布し、９０℃で１０分間乾燥させ、皮膜形成したガラス基板を２枚準備した。準備した１枚について、５０μｍのライン＆スペースパターンを持つフォトマスクを介して、ｉ線４０ｍＪ／ｃｍ２で露光した。次に、２３℃の０．１５質量％水酸化テトラメチルアンモニウム水溶液で７０秒間シャワー現像した後、純水で洗浄した。２３０℃で３０分間焼成して厚さ２．３μｍの皮膜付き基板１を得た。準備した２枚の皮膜形成したガラス基板の内、残りの１枚については、温度２３℃下で４８時間放置した後に、５０μｍのライン＆スペースパターンを持つフォトマスクを介して、ｉ線４０ｍＪ／ｃｍ２で露光した。次に、２３℃の０．１５質量％水酸化テトラメチルアンモニウム水溶液で７０秒間シャワー現像した後、純水で洗浄した。２３０℃で３０分間焼成して厚さ２．３μｍの皮膜付き基板２を得た。皮膜付き基板１、皮膜付き基板２の５０μｍパターンの線幅を光学顕微鏡にて計測し、下記評価基準にて評価した。
Ａ：４８時間での線幅変化が１μｍ未満
Ｂ：４８時間での線幅変化が１μｍ以上２μｍ未満
Ｃ：４８時間での線幅変化が２μｍ以上もしくはガラス部に残渣発生。 <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.
　＜閉塞性評価＞
　実施例１～７および比較例１～４により得られた感光性組成物を口金間ギャップ１００μｍのスリットコーターにてガラス基板上に塗布を行った。塗布完了後、６分間放置し、別のガラス基板に塗布し、得られた基板を目視にて観察し、下記評価基準にて評価した。
Ａ：塗布ムラなし
Ｂ：縦スジムラあり。 <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.
　製造例１（分散液（Ａ１）の調製）
　Ｃ．Ｉ．ピグメントグリーン５８（ＤＩＣ（株）製“ＦＡＳＴＧＥＮ”（登録商標）Ｇｒｅｅｎ　Ａ１１０）１５０ｇ、“ＢＹＫ”（登録商標）ＬＰＮ６９１９（ビックケミー社製、高分子分散剤溶液（６０質量％プロピレングリコールモノメチルエーテル溶液））１２５ｇ、“サイクロマー”（登録商標）ＡＣＡ２５０（ダイセル化学（株）製、４５質量％ジプロピレングリコールモノメチルエーテル溶液）１００ｇ、プロピレングリコールモノメチルエーテル（ＰＭＡ）６２５ｇを混合してスラリーを作製した。スラリーを入れたビーカーをダイノーミルとチューブでつなぎ、メディアとして直径０．５ｍｍのジルコニアビーズを使用して、周速１４ｍ／ｓで８時間の分散処理を行い、Ｃ．Ｉ．ピグメントグリーン５８分散液（Ａ１）を調製した。尚、分散液（Ａ１）はカルボキシル基を有しない。 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.
　製造例２（分散液（Ａ２）の調製）
　Ｃ．Ｉ．ピグメントグリーン５８にかえてＣ．Ｉ．ピグメントイエロー１５０（大日精化（株）製　“クロモファイン（登録商標）イエロー６２６６ＥＣ”）１５０ｇを用いたこと以外は製造例１と同様にして、Ｃ．Ｉ．ピグメントイエロー１５０分散液（Ａ２）を調製した。尚、分散液（Ａ２）はカルボキシル基を有しない。 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.
　製造例３（アルカリ可溶性樹脂溶液（Ｂ１）の合成）
　２０ｇのメタクリル酸、２０ｇのスチレン、８ｇのトリシクロデカニルメタクリレート、２０ｇのメタクリル酸メチル、３ｇの２，２’－アゾビス（２－メチルブチロニトリル）および１５０ｇのＰＧＭＥＡを重合容器中に仕込み、窒素雰囲気下で９０℃にて２時間撹拌してから液温を１００℃に上げ、さらに５時間反応させた。次に、重合容器を空気置換し、得られた反応溶液に１０ｇのメタクリル酸グリシジル、１．２ｇのジメチルベンジルアミンおよび０．２ｇのｐ－メトキシフェノールを添加して１１０℃で６時間撹拌させた。得られた溶液にＰＧＭＥＡを加えて希釈し、固形分３５質量％のアルカリ可溶性樹脂溶液（Ｂ１）を得た（アルカリ可溶性樹脂の二重結合当量１１７１ｇ／モル、トリシクロデカニル骨格を有するユニットの重量比率９．７質量％、酸成分としてはカルボキシル基のみ）。京都電子工業（株）製の電位差自動測定装置ＡＴ－６１０を用いて、０．１ｍｏｌ／Ｌ水酸化カリウム・エタノール溶液についてアルカリ可溶性樹脂の酸価を測定したところ、酸価は１０９．２（ｍｇＫＯＨ／ｇ）であった。また、ＧＰＣ装置を用いて、ポリスチレン換算の重量平均分子量を算出したところ、重量平均分子量は３１，４００であった。 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.
　製造例４（アルカリ可溶性樹脂溶液（Ｂ２）の合成）
　２０ｇのメタクリル酸、２０ｇのスチレン、１５ｇのトリシクロデカニルメタクリレート、２０ｇのメタクリル酸メチル、３ｇの２，２’－アゾビス（２－メチルブチロニトリル）および１５０ｇのＰＧＭＥＡを重合容器中に仕込み、窒素雰囲気下で９０℃にて２時間撹拌してから液温を１００℃に上げ、さらに５時間反応させた。次に、重合容器を空気置換し、得られた反応溶液に９ｇのメタクリル酸グリシジル、１．２ｇのジメチルベンジルアミンおよび０．２ｇのｐ－メトキシフェノールを添加して１１０℃で６時間撹拌させた。得られた溶液にＰＧＭＥＡを加えて希釈し、固形分３５質量％のアルカリ可溶性樹脂溶液（Ｂ２）を得た（アルカリ可溶性樹脂の二重結合当量１３９６ｇ／モル、トリシクロデカニル骨格を有するユニットの重量比率１７．０質量％、酸成分としてはカルボキシル基のみ）。京都電子工業（株）製の電位差自動測定装置ＡＴ－６１０を用いて、０．１ｍｏｌ／Ｌ水酸化カリウム・エタノール溶液についてアルカリ可溶性樹脂の酸価を測定したところ、酸価は１０６．８（ｍｇＫＯＨ／ｇ）であった。また、ＧＰＣ装置を用いて、ポリスチレン換算の重量平均分子量を算出したところ、重量平均分子量は１２，０００であった。 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.
　製造例５（アルカリ可溶性樹脂溶液（Ｂ３）の合成）
　２７ｇのメタクリル酸、１５ｇのスチレン、５ｇのトリシクロデカニルメタクリレート、１５ｇのメタクリル酸メチル、３ｇの２，２’－アゾビス（２－メチルブチロニトリル）および１５０ｇのＰＧＭＥＡを重合容器中に仕込み、窒素雰囲気下で９０℃にて２時間撹拌してから液温を１００℃に上げ、さらに５時間反応させた。次に、重合容器を空気置換し、得られた反応溶液に１３ｇのメタクリル酸グリシジル、１．２ｇのジメチルベンジルアミンおよび０．２ｇのｐ－メトキシフェノールを添加して１１０℃で６時間撹拌させた。得られた溶液にＰＧＭＥＡを加えて希釈し、固形分３５質量％のアルカリ可溶性樹脂溶液（Ｂ３）を得た（アルカリ可溶性樹脂の二重結合当量８６８ｇ／モル、トリシクロデカニル骨格を有するユニットの重量比率６．３質量％、酸成分としてはカルボキシル基のみ）。京都電子工業（株）製の電位差自動測定装置ＡＴ－６１０を用いて、０．１ｍｏｌ／Ｌ水酸化カリウム・エタノール溶液についてアルカリ可溶性樹脂の酸価を測定したところ、酸価は１５７．１（ｍｇＫＯＨ／ｇ）であった。また、ＧＰＣ装置を用いて、ポリスチレン換算の重量平均分子量を算出したところ、重量平均分子量は２８，９００であった。 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.
　製造例６（アルカリ可溶性樹脂溶液（Ｂ４）の合成）
　２０ｇのメタクリル酸、２０ｇのスチレン、７ｇのトリシクロデカニルメタクリレート、２０ｇのメタクリル酸メチル、３ｇの２，２’－アゾビス（２－メチルブチロニトリル）および１５０ｇのＰＧＭＥＡを重合容器中に仕込み、窒素雰囲気下で９０℃にて２時間撹拌してから液温を１００℃に上げ、さらに５時間反応させた。次に、重合容器を空気置換し、得られた反応溶液に１４ｇのメタクリル酸グリシジル、１．２ｇのジメチルベンジルアミンおよび０．２ｇのｐ－メトキシフェノールを添加して１１０℃で６時間撹拌させた。得られた溶液にＰＧＭＥＡを加えて希釈し、固形分３５質量％のアルカリ可溶性樹脂溶液（Ｂ４）を得た（アルカリ可溶性樹脂の二重結合当量８６７ｇ／モル、トリシクロデカニル骨格を有するユニットの重量比率８．２質量％、酸成分としてはカルボキシル基のみ）。京都電子工業（株）製の電位差自動測定装置ＡＴ－６１０を用いて、０．１ｍｏｌ／Ｌ水酸化カリウム・エタノール溶液についてアルカリ可溶性樹脂の酸価を測定したところ、酸価は８７．６（ｍｇＫＯＨ／ｇ）であった。また、ＧＰＣ装置を用いて、ポリスチレン換算の重量平均分子量を算出したところ、重量平均分子量は３２，３００であった。 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.
　（実施例１）
　５０ｍＬプラスチックボトルに、製造例１により得られた分散液Ａ１　６．１１ｇ、製造例２により得られた分散液Ａ２　２．０４ｇ、製造例３により得られたアルカリ可溶性樹脂溶液Ｂ１　４．４２ｇ、ラジカル重合性化合物Ｃ１　１．５７ｇ、光重合開始剤Ｄ１　０．０９ｇ、有機溶剤Ｅ１　１５．７８ｇを添加し、３時間撹拌して、感光性組成物（Ｆ１、Ｔ／Ｍ＝１３８７）を調製した。得られた感光性組成物について、前記方法により形状保持性評価を行ったところ、パターンへの乗り上げ部の高さＨは、１．３０μｍ、傾斜幅Ｌは１７．３μｍであった。また、前記方法により皮膜安定性評価を行ったところ、４８時間での線幅変化は１μｍ未満（Ａ評価）であった。また、前記方法により閉塞性評価を行ったところ、基板上に塗布ムラは見られなかった（Ａ評価）。また、有機溶剤Ｅ１の配合量のみを変更して、感光性組成物（Ｆ１、固形分濃度１８質量％）と固形分濃度のみが異なる２５質量％の感光性組成物を調製し、それぞれの粘度を東機産業（株）社製粘度計ＲＥ－２１５Ｌにて測定し、固形分濃度を１８質量％から２５質量％に変化させたときの固形分変化量当たりの粘度変化量Δη／ΔＷを評価したところ、０．５８であった。 (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.
　（実施例２～７、比較例１～４）
　分散液、アルカリ可溶性樹脂溶液、ラジカル重合性化合物、光重合開始剤、有機溶剤の種類と仕込み量を表１に記載のとおり変更したこと以外は実施例１と同様にして感光性組成物（Ｆ２～Ｆ１１）を得た。得られた感光性組成物を用いて、前記方法により評価した結果を表２にまとめた。 (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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
１　ガラス基板
２　パターン形状
３　感光性組成物からなる皮膜
Ｌ　傾斜幅
Ｈ　高さ 1 Glass substrate 2 Pattern shape 3 Film L made of photosensitive composition Gradient width H Height
　本発明の感光性組成物は、カラーフィルタ基板や指紋センサー、およびそれらを備えた表示装置、加飾用インク材料等に好適に使用できる。 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 (9)

  1. トリシクロデカニル骨格を有するアルカリ可溶性樹脂、ラジカル重合性化合物、光重合開始剤、色材および有機溶剤を含有する感光性組成物であって、前記トリシクロデカニル骨格を有するアルカリ可溶性樹脂の占める割合が固形分中２０質量％以上４０質量％以下であり、かつ前記感光性組成物の色材を除く固形分の総質量Ｔｇと前記感光性組成物の色材を除く固形分中に含まれるカルボキシル基のモル数Ｍの比率Ｔ／Ｍが１３００以上１６００以下を満たす感光性組成物。 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.
  2. 前記トリシクロデカニル骨格を有するアルカリ可溶性樹脂に含まれるトリシクロデカニル骨格を有するユニットの重量比率が、トリシクロデカニル骨格を有するアルカリ可溶性樹脂中２質量％以上１５質量％以下である請求項１に記載の感光性組成物。 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. 前記トリシクロデカニル骨格を有するアルカリ可溶性樹脂の重量平均分子量が２０，０００以上４０，０００以下である請求項１または２に記載の感光性組成物。 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.
  4. 前記トリシクロデカニル骨格を有するアルカリ可溶性樹脂の二重結合当量が５００以上２，０００以下である請求項１または２に記載の感光性組成物。 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.
  5. 固形分濃度を１８質量％から２５質量％に変化させたときの固形分変化質量ΔＷ（質量％）当たりの粘度変化量Δη（ｃＰ）が、０．５０以上０．７０以下である請求項１または２に記載の感光性組成物。 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.
  6. 請求項１または２に記載の感光性組成物の光硬化物を含む画素を有するカラーフィルタ基板。 A color filter substrate having pixels containing a photocured product of the photosensitive composition according to claim 1 or 2.
  7. 請求項１または２に記載の感光性組成物の光硬化物を有する指紋センサー。 A fingerprint sensor comprising a photocured product of the photosensitive composition according to claim 1 or 2.
  8. 請求項６に記載のカラーフィルタ基板を有する表示装置。 A display device comprising the color filter substrate according to claim 6 .
  9. 請求項７に記載の指紋センサーを有する表示装置。 A display device comprising the fingerprint sensor according to claim 7 .
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JP2002296775A (en) * 2001-03-30 2002-10-09 Dainippon Printing Co Ltd Photosensitive resin composition, color filter and liquid crystal panel
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