WO2007105644A1 - Photosensitive-resin layered product - Google Patents

Photosensitive-resin layered product Download PDF

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Publication number
WO2007105644A1
WO2007105644A1 PCT/JP2007/054694 JP2007054694W WO2007105644A1 WO 2007105644 A1 WO2007105644 A1 WO 2007105644A1 JP 2007054694 W JP2007054694 W JP 2007054694W WO 2007105644 A1 WO2007105644 A1 WO 2007105644A1
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WO
WIPO (PCT)
Prior art keywords
photosensitive resin
mass
alkali
soluble polymer
group
Prior art date
Application number
PCT/JP2007/054694
Other languages
French (fr)
Japanese (ja)
Inventor
Yuzo Kotani
Original Assignee
Asahi Kasei Emd Corporation
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 Asahi Kasei Emd Corporation filed Critical Asahi Kasei Emd Corporation
Priority to JP2008505117A priority Critical patent/JP4954194B2/en
Priority to CN2007800090843A priority patent/CN101401036B/en
Publication of WO2007105644A1 publication Critical patent/WO2007105644A1/en

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • 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
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • 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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask

Definitions

  • the present invention relates to a photosensitive resin laminate useful for manufacturing a substrate with a black matrix, a substrate with color pixels, and a color filter.
  • a liquid crystal display has a member that colors backlight light, generally called a color filter.
  • the color filter is composed of red, green, and blue color pixels and a black matrix that separates them.
  • the power required for colorization of color pixels The black matrix is usually arranged in a grid pattern between the color pixels for the purpose of preventing TFT malfunction, improving contrast, and preventing color mixing. .
  • liquid crystal displays have been required to have higher quality.
  • it is required to increase the color purity of the color pixel.
  • Increasing the color purity decreases the backlight transmittance and decreases the brightness.
  • Compensating for a decrease in the transmittance of the backlight light When the luminance of the backlight light is increased, the black matrix that separates the color pixels from the color pixels cannot completely block the knock light, and part of the light is transmitted.
  • the aperture, that is, the color pixel portion needs to be designed to be large in order to ensure the brightness of the panel, the black matrix tends to be thinned accordingly.
  • the black matrix has been manufactured by a metal thin film formed by sputtering, for example, chromium.
  • chromium for example, chromium
  • black matrix made of a resin containing a black pigment using a photolithography method is the mainstream. It is becoming.
  • the essential function of the rosin black matrix is that it has a high light-shielding property, it is very difficult to increase the sensitivity when it is produced using a photosensitive rosin.
  • the light shielding property is high and only a small amount of light reaches the bottom surface as compared with the surface, it is very difficult to ensure adhesion, particularly fine line adhesion, and line width stability during overdevelopment.
  • the color pixels are not as large as the black matrix, the sensitivity of the color pigments is significantly reduced because the colored pigments absorb at the exposure wavelength.
  • Patent Document 1 discloses a photopolymerizable black composition capable of obtaining a good black matrix pattern having a high optical density.
  • Patent Document 2 discloses a color filter forming material in which a specific photopolymerizable resin composition is laminated on a support film.
  • a resin black matrix is formed that has sufficient sensitivity, light-shielding properties, fine wire adhesion, line width stability during over-development, and simultaneously satisfies productivity. There was no disclosure of materials.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2004-69754
  • Patent Document 2 Japanese Patent Laid-Open No. 2005-208480
  • the present invention provides a photosensitive resin laminate excellent in sensitivity, light shielding property, fine wire adhesion, line width stability during over-development, transferability, and productivity in forming a resin black matrix. It is an object of the present invention to provide a method and a method for producing a black resin black matrix using the same. Furthermore, an object of the present invention is to provide a highly sensitive photosensitive resin laminate and a method for producing a color pixel using the same in forming color pixels.
  • the present invention is as follows. (1) At least a support layer and a photosensitive resin layer are laminated, and the photosensitive resin layer is 3 to 40% by mass of an alkali-soluble polymer represented by the following formula (I),
  • a photosensitive resin laminate comprising a photosensitive resin composition.
  • X is a group represented by the following formula ( ⁇ ⁇ )
  • Y is a residue excluding an acid anhydride group of dicarboxylic anhydride
  • Z is an acid of tetracarboxylic dianhydride. Residue excluding an anhydride group
  • n is an integer of 1 to 20.
  • R and R are each independently H or CH
  • Alkali-soluble polymer represented by formula (I): Alkali-soluble polymer (mass ratio) obtained by copolymerization of benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to L0,000 1: 5 to 16: 1
  • the photosensitive resin laminate according to (1) comprising the photosensitive resin composition.
  • Alkali-soluble polymer represented by the formula (I): alkali-soluble polymer (mass ratio) 1 copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 50,000 :
  • Alkali-soluble polymer represented by the formula (I): Alkali-soluble by copolymerization of benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to L00,000 Polymer and weight average molecular weight of 3,000 to 50,000 acrylic alkali-soluble polymer at least one kind selected from the group consisting of alkali-soluble polymer (mass ratio) 2: 1 to 16: 1 (1)
  • the photosensitive resin composition contains a compound represented by the following formula (III) as a photopolymerizable compound having an ethylenically unsaturated double bond: (1) to (4) The photosensitive resin laminate according to any one of the preceding items.
  • R, R and R each independently represent an H or CH group.
  • 3 4 5 3 6 is a divalent linking group selected from the group consisting of an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, and a phenyl group having 6 to 10 carbon atoms. Represents a group of )
  • a substrate with a color pixel comprising the photosensitive resin laminate according to any one of (1) to (4) in the order of at least a step of laminating a substrate, a step of exposing, and a step of developing. Production method.
  • a method for producing a substrate with a black matrix comprising at least a step of laminating the photosensitive resin laminate according to (7) on a substrate, an exposing step, a step of peeling a support layer, and a developing step.
  • a black matrix comprising, in order, at least the step of laminating the photosensitive resin laminate according to (7) on a substrate, the step of peeling the support layer, the step of exposing, and the step of developing.
  • a method for producing a color filter which includes a printing step of printing photosensitive color ink by an ink jet method.
  • the photosensitive resin laminate of the present invention is excellent in sensitivity, light-shielding property, fine wire adhesion, line width stability during over-development, transferability, and productivity when forming a resin black matrix. There is an effect.
  • the photosensitive resin laminate of the present invention has the effect of being very sensitive in forming color pixels.
  • the photosensitive resin layer in the photosensitive resin laminate of the present invention comprises a photosensitive resin composition.
  • a photosensitive resin composition When describing the blending amount of each component of the photosensitive resin composition, it is described in mass% when the total solid content in the photosensitive resin composition is 100%.
  • the photosensitive resin laminate of the present invention comprises an alkali-soluble polymer represented by the following formula (I) (hereinafter sometimes simply referred to as a compound) 3 to 3 in the photosensitive resin composition.
  • a compound represented by the following formula (I) (hereinafter sometimes simply referred to as a compound) 3 to 3 in the photosensitive resin composition.
  • the content is 3% by mass or more from the viewpoint of sensitivity, adhesion, and line width reproducibility, and 40% by mass or less from the viewpoint of transferability from the support layer to the substrate.
  • Transferability refers to the ability of the photosensitive resin layer of the present invention to be laminated to a substrate, and the photosensitive resin layer transferred to the substrate when the support layer is peeled off before or after exposure.
  • the content is preferably 5 to 30% by mass, more preferably 8 to 25% by mass, and still more preferably 8 to 20% by mass.
  • X is a group represented by the following formula ( ⁇ )
  • Y is a residue excluding the acid anhydride group of dicarboxylic anhydride
  • Z is an acid of tetracarboxylic dianhydride. Residue excluding an anhydride group
  • n is an integer of 1 to 20.
  • R and R are each independently H or CH
  • acid anhydride group refers to “one CO—O—CO— group”.
  • Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, Examples include chlorendic anhydride, methyltetrahydrophthalic anhydride, and dartaric anhydride.
  • examples of the tetracarboxylic dianhydride include pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride and the like.
  • An aromatic polyhydric carboxylic acid anhydride is mentioned.
  • the compound represented by the above formula (I) used in the present invention can be obtained, for example, by the method described in JP-A No. 2001-354735.
  • the compound represented by the above formula (I) has substantially no dicarboxylic acid anhydride residue in the polymerization chain, but has at its end. Therefore, unlike a compound having a dicarboxylic acid anhydride residue in the polymer chain, even at the same solid content concentration, the solution viscosity can be easily controlled to improve workability during coating and improve coating properties. In addition, the film thickness can be made uniform.
  • the compound represented by the above formula (I) used in the present invention has at least two ethylenically unsaturated double bonds capable of addition polymerization in the compound.
  • the photosensitive resin composition containing this compound is cured by addition polymerization by the action of the photopolymerization initiator even when the optical density is high when irradiated with light of a predetermined wavelength that activates the photopolymerization initiator. can do. This makes it possible to produce color filters with high R, G, and B colors with high display contrast.
  • this compound is used for forming a black matrix, this effect is remarkable in the relationship between light shielding properties and sensitivity.
  • the compound represented by the above formula (I) is usually used to increase the light shielding property and reduce the sensitivity. In this case, the sensitivity reduction can be kept low.
  • the photosensitive resin laminate of the present invention is obtained by copolymerizing benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to LOO, 000 in a photosensitive resin composition. 1 to 40% by mass of a potassium soluble polymer and at least one alkali-soluble polymer selected from the group consisting of acrylic alkaline soluble polymers having a weight average molecular weight of 3,000 to 50,000.
  • carbon black which is widely used as a black pigment, tends to be a liquid with poor thirotropic properties and poor fluidity when used in a photosensitive resin composition having a large surface area and dispersed in a pigment.
  • composition material 'Manufacturing' evaluation. Overseas trend ⁇ ", 1st edition, Information Organization Co., Ltd., May 31, 2005, p81-101).
  • the compound represented by the above formula (I) having excellent patterning characteristics and the alkali-soluble polymer having excellent pigment dispersion, coating stability, and transferability are blended together. Further, by forming a photosensitive resin laminate, a uniform photosensitive resin layer having a high light shielding property can be easily laminated on the substrate.
  • the photosensitive resin laminate of the present invention is obtained by copolymerizing benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 300,000 to L00, 000 in the photosensitive resin composition.
  • Alkali-soluble polymer and at least one alkali-soluble polymer selected from the group consisting of acrylic alkali-soluble polymers having a weight average molecular weight of 3,000 to 50,000 Contains 1-40% by weight of the child.
  • the content of the alkali-soluble polymer copolymerized with benzyl (meth) acrylate is 1 to 40% by mass.
  • the content is more preferably 5 to 40% by mass.
  • the content is more preferably 5% by mass or more, and the viewpoint power of adhesiveness and line width stability is more preferably 40% by mass or less.
  • the content is preferably 8-30% by mass, more preferably 10-25% by mass, and most preferably 10-18% by mass.
  • benzyl (meth) acrylate it is preferable to copolymerize 50 to 95% by mass of benzyl (meth) acrylate in the alkali-soluble polymer copolymerized with benzyl (meth) acrylate! /.
  • the copolymerization ratio of benzyl (meth) acrylate is preferably 90% by mass or less from the viewpoint of development speed, which is preferably 50% by mass or more, from the viewpoint of dispersibility of black pigment, development residue, and laminating property.
  • (Meth) acrylic acid The proportion of benzyl copolymerization is more preferably from 60 to 90 mass%, more preferably from 70 to 90 mass%.
  • the alkali-soluble polymer obtained by copolymerizing benzyl (meth) acrylate is preferably copolymerized with a monomer having a carboxyl group or a carboxylic anhydride group in the side chain.
  • Monomers having a carboxyl group or a carboxylic acid anhydride group in the side chain include, for example, (meth) acrylic acid, fumaric acid, cinnamate, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic Examples include acid half esters.
  • the copolymerization ratio of the monomer having a carboxyl group in the side chain is the dispersibility of the black pigment, which is preferably 5% by mass or more from the viewpoint of developability, and suppresses the black pigment from adhering to the substrate after development. From the viewpoint, 30% by mass or less is preferred! It is more preferable to copolymerize 5-20% by weight of U.
  • the alkali-soluble polymer obtained by copolymerizing benzyl (meth) acrylate can also be copolymerized with other monomers.
  • Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate Tert-Butyl (meth) acrylate, 2-ethyl Hexyl (meth) atarylate,
  • (Meth) acrylate having a hydroxyl group for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, (meth) having a cycloalkyl group
  • Atalylates such as cyclohexyl (meth) atrelate, isobornyl (meth) atalylate, dicyclopentatal (meth) atarylate, dicyclopentagel (meth) atarylate, adamantyl (meth) atalylate
  • Other examples include (meth) acrylamide, (meth) acrylonitrile, phenol (meth) acrylate, glycidyl methacrylate, and styrene.
  • the copolymerization ratio of the other monomer in the alkali-soluble polymer is preferably 5 to 30% by mass.
  • the copolymerization ratio depends on the dispersibility and lamination of the black pigment. From the viewpoint of heat resistance and chemical resistance, 5% by mass or more is preferable, and 30% by mass or less is preferable.
  • the copolymerization ratio is more preferably 5 to 15% by mass.
  • the weight average molecular weight of the alkali-soluble polymer copolymerized with benzyl (meth) acrylate is more preferably 3,000-50,000. From the viewpoint of adhesion, the molecular weight is more preferably not less than 3,000, more preferably not less than 3,000. Its weight average molecular weight force s 10,000 to 40,000 is more preferred power /!
  • the molecular weight was measured by Gel Permeation Chromatography (GPC) manufactured by JASCO Corporation.
  • the alkali-soluble polymer obtained by copolymerizing benzyl (meth) acrylate preferably has a carboxyl group content of 200 to 2,000 in terms of acid equivalent.
  • the acid equivalent refers to the mass of a linear polymer having 1 equivalent of a carboxyl group. From the viewpoint of developability, the acid equivalent is preferably 2,000 or less. From the viewpoint of suppressing the black pigment from adhering to the substrate after development, the acid equivalent is More than 200 power! / ⁇ . Its acid equivalent is more preferably 400 to 900 force, more preferably 500 to 800 force.
  • the acid equivalent is measured by the potentiometric titration method using Hiranuma Automatic Titration System (COM-55 5) manufactured by Hiranuma Sangyo Co., Ltd. and 0.1 mol ImolZL sodium hydroxide.
  • the alkali-soluble polymer copolymerized with benzyl (meth) acrylate is peroxidized into a solution obtained by diluting a mixture of the above-mentioned various monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to carry out the synthesis by adding an appropriate amount of a radical polymerization initiator such as benzoyl, azobisisobutyric-tolyl and the like, followed by superheated stirring. In some cases, a part of the mixture is added dropwise to the reaction solution. After the reaction is complete, a solvent may be added to adjust the concentration to the desired level.
  • a synthesis means in addition to solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization may be used.
  • the content of the acrylic alkali-soluble polymer having a weight average molecular weight of 3,000 to 50,000 is 1 to 40% by mass. It is 1% by mass or more from the viewpoint of transferability from the support layer to the substrate and lamination, and 40% by mass or less from the viewpoints of sensitivity, adhesion, and line width stability.
  • the content is preferably 5 to 40% by mass, more preferably 8 to 20% by mass, and still more preferably 8 to 15% by mass.
  • the weight average molecular weight is 3,000 or more from the viewpoint of maintaining moderate alkali developability and adhesion, which are preferred from the viewpoint of dispersion stability of pigments of 50,000 or less.
  • the weight average molecular weight is more preferably 5,000 or more and 30,000 or less, and still more preferably 10,000 or more and 30,000 or less.
  • the molecular weight can be determined by the same measurement method as described above.
  • An acrylic alkali-soluble polymer having a weight average molecular weight of 3,000 to 50,000 preferably has a carboxyl group content of 200 to 2,000 in terms of acid equivalent.
  • the acid equivalent refers to the mass of a linear polymer having 1 equivalent of a carboxyl group.
  • the acid equivalent is preferably 2,000 or less from the viewpoint of developability. From the viewpoint of suppressing the black pigment from adhering to the substrate after development, the acid equivalent is preferably 200 or more.
  • the acid equivalent is preferably 300 to 900, more preferably 400 to 800.
  • the acid equivalent can be determined by the same measurement method as described above.
  • An acrylic alkali-soluble polymer having a weight average molecular weight of 3,000 to 50,000 is an alkyl (meth) acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n -Butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate
  • a hydroxyl group in the side chain (Meth) acrylate for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate,
  • (Meth) acrylate having alicyclic side chain for example, cyclohexyl (meth) acrylate, isobolol (meth) acrylate, dicyclopental (meth) acrylate, dicyclopentadiol (meth) Atalylate, adamantyl (meth) atarylate, and others, for example, (meth) acrylamide, (meth) acrylonitrile, phenol (meth) acrylate, glycidyl (meth) acrylate, styrene power and one or more compounds selected Examples thereof include compounds having a carboxylic acid, such as alkali-soluble polymers copolymerized with (meth) acrylic acid.
  • a polymer having a molecular weight of 10,000 to 30,000 obtained by copolymerizing styrene, methyl methacrylate and methacrylic acid is preferable.
  • the mass ratio is 1: 5 or more from the viewpoint of sensitivity, adhesion, and line width reproducibility, and 16: 1 or less from the viewpoint of coating property to the support layer and transferability.
  • the mass ratio is preferably 1: 5 to 5: 1. In view of sensitivity, adhesion, and line width reproducibility, 1: 5 or more is preferable. From the viewpoint of coating property to the support layer and transferability, 5: 1 or less is more preferable. It is more preferable that the ratio is 1: 3 to 3: 1.
  • Re-soluble polymer (mass ratio) 1: 5 to 16: 1.
  • the mass ratio is 1: 5 or more from the viewpoint of sensitivity, adhesion, and line width reproducibility, and is 16: 1 or less from the viewpoint of coating property to the support layer and transferability.
  • the mass ratio is preferably 1: 5 to 5: 1. In view of sensitivity, adhesion, and line width reproducibility, 1: 5 or more is preferable. A ratio of 5: 1 or less is more preferable from the viewpoint of coating property to the support layer and transferability. A ratio of 1: 3 to 3: 1 is more preferable.
  • the alkali-soluble polymer represented by the above formula (I): an acrylic alkali-soluble polymer (mass ratio) having a weight average molecular weight of 3,000 to 50,000, 000 1: 5 to 16: 1 It is.
  • the mass ratio is preferably 1: 3 to 5: 1. From the viewpoint of sensitivity, adhesion, and line width stability, 1: 3 or more is preferable. From the viewpoint of coatability to the support layer and transferability, 5: 1 or less is preferable. 1: 1 to 3: 1 is more preferable.
  • the photosensitive resin composition has an alkali-soluble polymer copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 and a weight average molecular weight.
  • alkali-soluble polymer selected from the group consisting of acrylic alkali-soluble polymers of 3,000-50,000, heat resistance, black matrix cross-sectional shape, chemical resistance, color pigment
  • other alkali-soluble polymers can be used in combination.
  • alkali-soluble polymers include carboxymethylcellulose, carboxyethylcellulose, force norepropoxypropenorenosellose, hydroxymethinorecenorelose, hydroxyethinoresenorelose, and hydroxypropylcellulose with a polybasic acid anhydride.
  • Examples thereof include cellulose resin and novolac resin obtained by reacting products.
  • the photosensitive resin laminate of the present invention contains 3 to 25% by mass of a photopolymerizable compound having an ethylenically unsaturated double bond in the photosensitive resin composition. From the viewpoint of developability, it is 3% by mass or more, and from the viewpoint of adhesion, it is 25% by mass or less. By setting it to 25% by mass or less, an appropriate development time can be secured, and sufficiently stable adhesion can be secured.
  • the content is more preferably 5 to 20% by mass, and further preferably 5 to 15% by mass.
  • the photopolymerizable compound having an ethylenically unsaturated double bond preferably includes a compound represented by the following formula (I). Its content is photosensitive resin composition from the viewpoint of adhesion From the viewpoint of transferability, 2% by mass or more based on the total solid content in the product is preferable. 20% by mass or less is preferable.
  • R 1, R and R each independently represent an H or CH group.
  • 3 4 5 3 6 is a divalent linking group selected from the group consisting of an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, and a phenyl group having 6 to 10 carbon atoms.
  • succinic acid-modified pentaerythritol tritalylate is preferable.
  • Examples of the photopolymerizable compound having an ethylenically unsaturated double bond other than the compound represented by the above formula ( ⁇ ) include, for example, an average of 2 mol of propylene oxide and an average of 6 mol at both ends of bisphenol A, respectively.
  • a half ester compound of 2-hydroxyethyl (meth) acrylate with 1 to 3 moles of ethylene oxide and hexahydrophthalic acid, 2-hydroxy shetyl (meth) acrylate A half-ester compound of succinic acid with a compound with 1 to 3 moles of ethylene oxide added thereto, and a compound with 1 to 3 moles of ethylene oxide with 2-hydroxyethyl (meth) acrylate and isophthalic acid.
  • a half ester compound a compound obtained by adding 1 to 3 moles of ethylene oxide to 2-hydroxychetyl (meth) acrylate and a half ester compound of terephthalic acid.
  • a diisocyanate compound such as hexamethylene diisocyanate, tolylene diisocyanate, or 2,2,4 trimethylhexamethylene diisocyanate, and one molecule
  • a diisocyanate compound such as hexamethylene diisocyanate, tolylene diisocyanate, or 2,2,4 trimethylhexamethylene diisocyanate
  • a urethane compound obtained by reacting a compound having a hydroxyl group and a (meth) acrylic group, for example, 2-hydroxypropyl acrylate, oligopropylene glycol monomethacrylate.
  • hexamethylene diisocyanate and oligopropylene glycol monometatalylate Nippon Yushi Co., Ltd., Bremer PP100
  • the compound part obtained by making 0) react can be mentioned.
  • the photosensitive resin laminate of the present invention contains 0.1 to 20% by mass of a photopolymerization initiator in the photosensitive resin composition. From the viewpoint of sensitivity and adhesion, it is 0.1% by mass or more, and from the viewpoint of line width reproducibility, it is 20% by mass or less. The content is more preferably 1 to 5% by mass, more preferably 1 to 10% by mass.
  • the photopolymerization initiator is preferably an oxime ester compound. Specifically Are oxime esters such as 1-phenol-1,2-propanedione-2-O-benzoyloxime, and 1-fluoro-1,2-propanedione-2- (O ethoxycarbon) oxime.
  • oxime esters such as 1-phenol-1,2-propanedione-2-O-benzoyloxime, and 1-fluoro-1,2-propanedione-2- (O ethoxycarbon) oxime.
  • the compounds described in JP-T-2004-534797 can be raised. Among these, a compound represented by the following formula (IV) is preferable.
  • the photosensitive resin laminate of the present invention may be used in combination with a photopolymerization initiator, a sensitizer, a chain transfer agent, and the like other than the above formula (IV) in the photosensitive resin composition. good.
  • Examples of the photopolymerization initiator other than the above formula (IV) include the following. Thioxanthone, 2, 4 Jetylthioxanthone, Isopropyl thixanthone, 2 Chloxone Thioxanthone, 2, 4, 5 Triarynoreidazonole dimers, for example, 2- (o black mouth phenol) — 4, 5 Diphenol-Lumimidazolnimer, 2— (o Black Mole), 4, 5 — Bis (m-methoxyphenol) imidazole Lunimer, 2— (p-methoxyphenol) 4, 5 —Gihue-Louimidazolnimer.
  • p-aminophenol ketones such as p-aminominobenzophenone, p-butylaminophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p, monobis (ethylamino) benzophenone, p, p, Bis (dimethylamino) benzophenone [Michler's ketone], p, p, bis (jetylamino) ben Zofenone, p, p'-bis (dibutylamino) benzophenone.
  • quinones for example, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, aromatic ketones, for example, benzoin ethers such as benzophenone, benzoin, benzoin methyl ether, and benzoin ethyl ether.
  • aromatic ketones for example, benzoin ethers such as benzophenone, benzoin, benzoin methyl ether, and benzoin ethyl ether.
  • Atalidine compounds such as 9-phenol atalidine.
  • Triazine compounds such as 2, 4, 6 trichloro s-triazine, 2 phe- —4, 6 bis (trichloromethyl) s triazine, 2— (p-methoxyphenol 4, 6-bis (trichloromethyl) ) S triazine, 2— (p-tolyl) 4, 6 bis (trichloromethyl) — s triazine, 2 pipetyl 4, 6 bis (trichloromethyl) s triazine, 2, 4 — bis (trichloromethyl) 6 —Styryl 1 s triazine, 2— (Naphtho 1-yl) 4,6 bis (trichloromethyl) s Triazine, 2— (4-methoxy 1 naphth 1-yl) 4,6 bis (trichloromethyl) s Triazine, 2, 4 Trichloromethyl mono (pipetyl) 6-Triazine, 2, 4 Trichloromethyl (4'-methoxystyryl) 6 Tria
  • sensitizers include N-aryglycine, mercaptotriazole derivatives, mercaptotetrazole derivatives, mercaptothiadiazole derivatives, and chain transfer agents such as hexanedithiol, decandithiol, and 1,4 butanediolbis.
  • the photosensitive resin laminate of the present invention contains 40 to 70 mass% of a coloring pigment in the photosensitive resin composition.
  • the light-shielding viewpoint power is 40% by mass or more, and it is 70% by mass or less from the viewpoints of transferability, black matrix adhesion, line width stability, and shape. Its content is preferably 45 to 65% by mass, more preferably 50 to 65% by mass.
  • Examples of the coloring pigment include organic pigments such as azo, phthalocyanine, indigo, anthraquinone, perylene, quinacridone, methine'azomethine, and isoindolinone, carbon blacks, titanium black, There are inorganic pigments such as titanium oxynitride, black low-order titanium oxide, dulphite powder, iron black, and copper oxide, and a plurality of pigments may be included. These pigments may be subjected to a surface treatment to increase the dispersibility in the photosensitive resin composition or to increase the electric resistance value.
  • organic pigments such as azo, phthalocyanine, indigo, anthraquinone, perylene, quinacridone, methine'azomethine, and isoindolinone
  • carbon blacks titanium black
  • inorganic pigments such as titanium oxynitride, black low-order titanium oxide, dulphite powder, iron black, and copper oxide, and a plurality of pigments
  • organic pigments examples include compounds classified as Pigments in the Color Index (CI; published by The Society of Dyers and Colors), and specifically the following Color Index listed with (CI) number. Listed below.
  • CI Pigment Red 9 CI Big Red 97, CI Big Red 105, CI Big Red 122, CI Big Red 123, CI Big Red 144, CI Pigment Red 149, CI Big Red 166 CI Pigment Red 168, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Tread 192, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Red 265.
  • CI Pigment Orange 13 CI Pigment Orange 31, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigmento Range 42, CI Pigment Orange 43, CI Pigment Orange 51 CI pigment orange 55, CI pigment orange 59, CI pigment orange 61, CI pigment orange 64, CI pigment orange 65, CI pigment orange 71, CI pigment orange 73.
  • Examples of the dye include fuchsin, phthalocyanine green, auramin base, calcidoside green S, paramagenta, crystal violet, methyl orange, Nile Blue 1B, Victoria blue, malachite green (Eisen, Hodogaya Chemical Co., Ltd.) (Registered trademark) MALACHITE GREEN), Basic Blue 20, Diamond Green (Hozengaya Chemical Co., Ltd. Aizen (registered trademark) DIAMOND GREEN GH) and the like.
  • the photosensitive resin laminate of the present invention is useful as a black matrix forming material when the color pigment is a black pigment.
  • black pigments include those that are black among the colored substances listed above.
  • organic pigments such as CI pigment black 1, CI pigment black 7, etc.
  • Powerful inorganic pigments include carbon blacks, titanium black, titanium oxynitride, black low-order titanium oxide, graphite powder, iron black , Copper oxide, and the like.
  • metal oxides such as a, Sr, Ba, Pd, Ag, Cd, In, Sn, Sb, Hg, Pb, Bi, Si, and Al, composite oxides, metal sulfides, metal lead sulfate, or metal carbonate Inorganic pigments such as salts can also be used.
  • Carbon black is preferred from the viewpoints of light shielding properties and sensitivity to black matrix, resolution, and adhesion. From the viewpoint of black matrix insulation, titanium black is preferred.
  • At least one carbon black exemplified below can be used.
  • Examples of carbon blacks manufactured by Cancarb may include THERMAX N990, N991, N907, and N908.
  • Asahi Carbon's carbon blacks include Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-2200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60 , Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15.
  • Degussa carbon black includes ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2V, ColorBlackFwl, ColorBlack Fwl8, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printexl40U, Printexl40V I can do it.
  • Carbon blacks manufactured by Cabot Corporation include Regal (registered trademark), Black Pearls (registered trademark), Elftex (registered trademark), and Monarch (registered trademark).
  • Carbon blacks from Colombian Chemical Corporation include Raven 780, Raven 890, Raven 1020, Raven 1040, Raven 1255, Raven 1500, Raven 5000, Raven 5250. I can do it.
  • the photosensitive resin composition may contain a dispersant and the like.
  • the photosensitive resin laminate can be produced by coating the photosensitive resin composition on the support layer, but the black pigment is previously dispersed in a solvent with a dispersant or the like and added. It can also be used as a photosensitive resin composition, which can be applied to the support layer to form a photosensitive resin layer.
  • Examples of the dispersant include carboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, Examples thereof include polysiloxanes, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) and a polyester having a free carboxylic acid group, and salts thereof. Further, a polymer dispersant having a basic functional group described in JP-A-2005-25169 can be used.
  • Disperbykl60, Disperbykl61, Disperby ykl62, Disperbykl63, Disperbvkl64, Disperbykl66 manufactured by Bicchem Corporation, and SOLSP manufactured by Geneca ERSE20000, SOLSPERSE24000, SOLSPERSE27000, SOLSPERSE28 000, SOLSPERSE32500 can be used.
  • the alkali-soluble polymer used in the present invention, the alkali-soluble polymer copolymerized with the above-mentioned benzyl (meth) acrylate, and other alkali-soluble polymers also have a function as a pigment dispersant.
  • the content in the case of containing a dispersant is preferably 0.1 to 15% by mass. From the viewpoint of adhesion, the power of 0.1% or more being preferred is preferably 15% by mass or less. More preferably rather is 1 to 10 mass 0/0.
  • ion-active activators such as polycarboxylic acid type polymer activators and polysulfonic acid type polymer activators, and non-ionic activators such as polyoxyethylene and polyoxylene block polymers , And can be used as a dispersion aid together with the above-described dispersant.
  • black pigments particularly carbon black
  • a resin or modified with a low molecular weight compound in consideration of dispersibility, insulation, and the like.
  • the resin used for the surface modification include polymers having a functional group capable of reacting with a carboxyl group on the surface of carbon black, such as polycarbopositimide and epoxy resin.
  • the low molecular weight compound include substituted benzene diazo-um compounds and substituted aralkyl diazo-um compounds.
  • the dispersant, method, etc. can be used.
  • the photosensitive resin composition may contain a coloring dye that develops color upon irradiation with light.
  • a coloring dye that develops color upon irradiation with light.
  • the coloring dye used include a combination of a leuco dye or a fluoran dye and a halogen compound.
  • the coloring dye can be blended in an appropriate amount depending on the desired OD value and color purity of the color pixel.
  • leuco dye examples include tris (4-dimethylamino-2-methylphenol) methane [leuco crystal violet].
  • halogen compound examples include amyl bromide, isoamyl bromide, odorous isoprene, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethyl phenol. Ninoles norephone, carbon tetrabromide, tris (2,3 dibromopropyl) phosphate, trichloro-acetoamide, amyl iodide, isobutyl iodide, 1, 1, 1-triclo-ortho-2, 2-bis (p chlorophe- E) ethane, hexachloroethane, triazine compounds and the like.
  • triazine compound examples include 2, 4, 6 tris (trichloromethyl) s triazine, 2
  • color developing dyes combinations of tribromomethyl phenol sulfone and leuco dyes, and combinations of triazine compounds and leuco dyes are useful.
  • the photosensitive resin composition may contain a radical polymerization inhibitor in order to improve thermal stability and storage stability.
  • radical polymerization inhibitors include ⁇ -methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2, 6-di-tert-butyl-p-cresol, 2, 2 , 1 Methylene bis (4-ethyl 6-tert-butyl phenol), 2, 2'-methylene bis (4-methyl-6- tert butyl phenol), triethylene glycol bis [3- (3-tert-butyl 5-methyl 4-hydroxy phenol] -Le) propionate] (IRGANOX245 manufactured by Ciba 'Specialty' Chemicals), diphenylnitrosamine and the like. IRGANOX245 is preferred because it is compatible with low sensitivity reduction and good storage stability.
  • a plasticizer may be contained as necessary.
  • plasticizers include phthalates such as jetyl phthalate, p-toluenesulfonamide, polypropylene glycol, polyethylene glycol monoalkyl ether, polyalkyleneoxide-modified bisphenol A derivatives such as bisphenol.
  • examples include an ethylene oxide adduct and propylene oxide adduct of A.
  • a preferable amount when the plasticizer is contained is 0.1 to 5% by mass. In view of the flexibility of the photosensitive resin layer and the viewpoint power to suppress chip jumping and cracking at the time of cutting after lamination, 0.1% by mass or more is preferable, and 5% by mass or less is preferable.
  • the photosensitive resin composition may contain a silane coupling agent.
  • Silane coupling agents include vinyl, epoxy, styryl, methacryloxy, and attaryloxy. And compounds having a polar group such as a group, amino group, ureido group, black propyl group, mercapto group, sulfide group, isocyanate group, imidazolyl group, and alkoxysilyl group in the molecule.
  • Shin-Etsu Silicone Co., Ltd. KBM-1003, KB E-1003, KBM-403, KBE-403, KBM-502, KBE-502, KBM-503, KBE-503, KBM-603, KBE — 603, KBM-903, KBE-903, KBE-585, KBM-802, KBE-846, KBE-9007, and the imidazolesilane compound described in JP-A-2004-280057.
  • the blending amount can be appropriately selected in consideration of the effect of adhesion and the adhesion of residues to the substrate after development, but it is preferable to include it in the range of 0.01 to 1% by mass.
  • the photosensitive resin laminate of the present invention can be produced by coating a photosensitive resin layer comprising a photosensitive resin composition on a support layer.
  • the support layer used here is preferably a transparent layer that transmits active light.
  • the support layer that transmits active light include polyethylene terephthalate film, polybutyl alcohol film, polybutyl alcohol film, vinyl chloride copolymer film, polyvinyl chloride film, polyvinylidene chloride copolymer film, Examples include polymethyl methacrylate copolymer film, polystyrene film, polyacrylo-tril film, styrene copolymer film, polyamide film, cellulose derivative film, triacetyl cellulose film, and polypropylene film. As these films, those stretched as necessary can be used.
  • Solvents include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl enoate ethere, ethylene glycol monomono propenoate ethere, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl etherenole, ethylene glycol Norési mouth pinoleatenore, propylene glycol monoremonomethinoleatenore, propyleneglycolenoremonoethylenoatere, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol jetyl ether, diethylene glycol Cornole Monomethinoreatenore, Diethylene Glycole Monolechinenoreatenore, Diethylene Glicono-resin
  • Methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoint of toxicity and drying properties when applied to the support layer.
  • Coloring pigments particularly the dispersion stability of black pigments, and the above formula (I) used in the present invention.
  • propylene glycol monomethyl etherate is preferred.
  • methyl ethyl ketone, methyl isobutyl ketone, etc. and PGMEA may be mixed at an appropriate ratio.
  • PGMEA in which a black pigment is preliminarily dispersed
  • PGMEA in which an alkali-soluble polymer of the above formula (I) is preliminarily dissolved
  • methacrylic acid having a weight average molecular weight of 3,000 to 100,000 and 00, respectively.
  • a photopolymerizable compound having an unsaturated double bond, a photopolymerization initiator, and other various additives are mixed and appropriately diluted with a solvent such as methyl ethyl ketone or PGMEA, and applied to the support layer. It can be prepared as a photosensitive resin composition solution having good fabric drying properties.
  • the haze of the support layer is preferably 5.0 or less. More preferably, it is 2.0 or less, and more preferably 1.0 or less.
  • the thickness of the support layer is generally 10 to 100 / ⁇ ⁇ because it is necessary to maintain the strength and strength, which is advantageous in terms of image forming property and economical efficiency.
  • a protective layer can be laminated on the surface of the photosensitive resin layer opposite to the support layer, if necessary. It is preferable that the adhesive force between the protective layer and the photosensitive resin layer is sufficiently smaller than the adhesive force between the support layer and the photosensitive resin layer, and it can be easily peeled off.
  • a protective layer include polyethylene film, polyethylene terephthalate film, polypropylene film, stretched polypropylene film (for example, Oji Paper Co., Ltd. ⁇ -200C, E-200A, etc.), and release-treated polyethylene. Examples include terephthalate film.
  • the preferred thickness of the protective layer is 15-50 / ⁇ ⁇ . From the viewpoint of smooth surface production, a thickness of 15 m or more is preferable, and from the viewpoint of lamination with a photosensitive resin layer and winding property, 50 / z m or less is preferable.
  • the photosensitive resin laminate of the present invention can be prepared by the following method.
  • a photosensitive resin composition As a photosensitive resin composition, an appropriate amount of an alkali-soluble polymer, a photopolymerizable compound having an ethylenically unsaturated double bond, a photopolymerization initiator, a color pigment, etc., so as to have a viscosity power of ⁇ to several tens cps A photosensitive resin composition solution is prepared by mixing with the above solvent.
  • the photosensitive resin composition solution is applied onto a 20 ⁇ m thick transparent polyester film to be a support layer and dried to form a photosensitive resin layer.
  • Application is performed using an apparatus according to the application area, application speed, and the like. Examples of the coating apparatus include a blade coater, a bar coater, and a gravure coater that are useful for a small area.
  • Capillary 1 ⁇ Co 1 ⁇ Ta ' ⁇ Raging and Rising Co ⁇ Ta' ⁇ , Slot Daiko 1 ⁇ Ta ' ⁇ "Rip Collector, Open Type Comb coaters and gravure coaters can be selected, and the drying temperature can be selected appropriately according to the solvent. It is preferable to dry at a temperature not higher than the temperature at which the dimensional stability of the support layer can be secured. 60-120 ° C is preferred. It is preferable that the drying time is longer than the degree at which the solvent can be sufficiently dried and the solvent is dried at a speed at which the applied surface force can be evaporated uniformly.
  • the dimensional stability of the support layer is not more than the extent that the dimensional stability cannot be ensured and the workability is not significantly impaired.
  • the drying means is a small area, a casting method or a hot-air circulating drying furnace can be used. In order to dry it through a drying chamber of several meters or more, it can be dried by blowing hot air on the coated surface or the supporting layer, or by passing it through the upper supporting layer of a heated roll. Hot air nozzle
  • a polyethylene film to be a protective layer is laminated and laminated.
  • the thickness of the photosensitive resin layer is preferably 0.3 m or more from the light shielding property of the black matrix and the film thickness accuracy during coating. Moreover, it is preferable that it is 4.5 / zm or less from the flatness when it is used for a color filter.
  • the height of the black matrix is preferably 4.5 m or less because the influence on the orientation of the liquid crystal can be reduced, the overcoat layer can be thinned, and the overall thickness of the color filter can be reduced.
  • the thickness of the photosensitive resin layer is more preferably 0.3 to 2111, and still more preferably 0.3 to 0.8 m.
  • the black matrix described in the present invention can be formed by the following method using the above-described photosensitive resin laminate.
  • the above photosensitive resin laminate is laminated (thermocompression bonding) on a glass substrate.
  • the glass substrate is preferably preheated.
  • the preheating temperature of the glass substrate is preferably 150 ° C. or lower from the viewpoint of laminating properties and the heat resistance of the support layer, which is preferably 100 ° C. or higher from the viewpoint of suppressing air entrained during lamination and ensuring sufficient adhesion. More preferably, it is 110 ° C or higher and 140 ° C or lower
  • the support layer may be peeled off before exposure.
  • the amount of the initiator and the amount of the compound represented by the above formula (I) included in the present invention are appropriately adjusted to design with high sensitivity. It is preferable to do.
  • the effect of the support layer on the sensitivity is preferably designed to be very sensitive compared to exposure through a large support layer.
  • a step of laminating a photosensitive resin laminate containing 8 to 20% by mass of a photopolymerization initiator on a substrate, a support layer It is preferable to manufacture a black matrix by a method for manufacturing a substrate with a black matrix, which is characterized by sequentially performing a peeling step, an exposing step, and a developing step.
  • a transparent substrate such as a glass substrate is preferable.
  • the above-mentioned weight average molecular weight in the photosensitive resin composition is 3, since the problem of transferability where the exposed portion sticks to the support layer and the substrate force peels off is avoided.
  • the compounding ratio of at least one alkali-soluble polymer selected from the group can be kept low, and the compounding amount of the compound represented by the above formula (I) can be increased. This is preferable from the viewpoint of sensitivity.
  • the unexposed area strongly adheres to the support layer, so that an alkali-soluble highly copolymerized benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000.
  • the blending ratio of at least one alkali-soluble polymer selected from the group consisting of acrylic alkali-soluble polymers having a molecular weight and a weight average molecular weight of 3,00 0-50,000 is 1% by mass or more. From the viewpoint, it is 40% by mass or less. Preferably it is 1-15 mass%, More preferably, it is 1-10 mass%, More preferably, it is 1-5 mass%. Similarly, since the unexposed portion strongly adheres to the support layer, the compounding amount of the compound represented by the formula (I) is 40% by mass or less, and 3% by mass or more from the viewpoint of sensitivity. . Preferably it is 10-40 mass%, More preferably, it is 15-40 mass%, More preferably, it is 20-40 mass%.
  • alkaline aqueous solutions include sodium carbonate aqueous solution, potassium carbonate aqueous solution, and potassium hydroxide aqueous solution.
  • alkaline aqueous solutions include sodium carbonate aqueous solution, potassium carbonate aqueous solution, and potassium hydroxide aqueous solution.
  • alkaline aqueous solutions are selected according to the characteristics of the photosensitive resin layer.
  • a 0.1 to 3% by weight aqueous sodium carbonate solution and a 0.03 to 0.1% by weight aqueous potassium hydroxide solution are used.
  • Another developer is an alkaline aqueous solution having a different alkalinity from the developer used when first developing the photosensitive resin layer, an acidic developer, or a developer containing an organic solvent.
  • the composition of the photosensitive resin layer can be appropriately selected according to the developer.
  • the photosensitive resin layer in the unexposed area remaining undeveloped, the colored pigment, and the black pigment can be physically removed by a method such as high pressure water washing. 0. A washing pressure of 2 MPa or more is effective.
  • the color filter of the present invention is covered with at least the black matrix of the glass substrate with the black matrix. It can be produced by forming red, blue, and green power pixels with a photosensitive or photosensitive color ink.
  • the shape of the black matrix is generally a lattice shape surrounding the color pixels.
  • the pattern width of each side of the lattice is 5 to 50 ⁇ m, and the interval between lattice points is 30 to 500 ⁇ m.
  • the red 'blue' and green color pixels are produced by photolithography using a color resist such as the photosensitive resin laminate or liquid resist of the present invention, or ink jets using color inks. It can be produced by a method or a printing method, or various methods can be used.
  • the ink jet method is a method of injecting color ink by an ink jet method using a black matrix formed on a glass substrate as a weir.
  • the inkjet method does not require an exposure process that requires an expensive mask, does not require a development process, can form a pixel pattern regardless of unevenness, and improves the yield. This is preferable because a pixel pattern can be easily formed.
  • a composition having a pigment and a dye exemplified as a coloring substance, a photopolymerizable compound having an ethylenically unsaturated double bond, a heat or a photopolymerizable initiator, and having a viscosity adjusted appropriately with a solvent is used.
  • the colored ink described in Example 1 of JP-A-2004-213033 can be used.
  • the black matrix is preferably color repellent ink. Due to this property, due to the problem of ink landing accuracy, the color ink on the black matrix can also slide down the weir to fill the space for the color pixels.
  • a photosensitive resin laminate laminated on a transparent support layer is used.
  • the photosensitive resin composition is applied directly to a glass substrate, dried, and then exposed to development through a photomask, and then applied to glass without using a drying step.
  • This is a preferable method in that the film thickness non-uniformity does not occur and the transparent support layer prevents contact between the photopolymerizable resin composition and the photomask, so that the photomask is not easily contaminated.
  • a black photosensitive resin laminate is formed on a glass substrate after color pixels having a thickness of about 2 m are formed on the glass substrate.
  • a method of laminating the film and exposing the glass substrate side force is also known (see Japanese Patent No. 3409925). Forming the black matrix in this order has the advantage that the black matrix is originally formed only between the pixels, so that the alignment of the color pixels and the black matrix can be omitted.
  • thermoplastic resin layer and an intermediate layer are laminated on a support layer having a thickness of 70 to 100 m or more, and further, Laminating a photosensitive resin layer results in a complex layer structure.
  • the thermoplastic resin layer is embedded for embedding, and the intermediate layer is provided to prevent contact between the thickened support layer and the Z or thermoplastic resin layer after exposure after peeling the photosensitive resin layer and oxygen.
  • Photosensitive resin laminate of the present invention By using a body, it is possible to form a black matrix in advance because it has excellent line width reproducibility and adhesion, so that the layer structure is simplified and the support layer has an exposure wavelength of 20 m or less. A thing with little absorption scattering can be used. By using a high-quality support layer, line width stability, pattern shape, and linearity are further improved.
  • Compound 1 represented by the above formula (I) was synthesized according to the method described in JP-A-2001-354735.
  • compound 1 is the compound represented by the above formula (I)
  • X is a group represented by the above formula ( ⁇ ⁇ )
  • Y is 1, 2, 3, 6— Tetrahydrophthalic anhydride Power residue after removal of acid anhydride group (—CO—O—CO—)
  • Z is from 3, 3 ', 4, 4' monobenzophenone tetracarboxylic dianhydride to acid anhydride It corresponds to a compound having a YZZ molar ratio of 50.0 / 50.0.
  • This compound 1 was made into an alkali-soluble polymer, adjusted so that the solid content concentration in PGMEA was 40% by mass, and used to prepare the following photosensitive resin composition solution.
  • Each component of the photosensitive resin composition was mixed in the ratio shown in Table 1 to obtain a photosensitive resin composition solution having a solid content of 10% by mass using methyl ethyl ketone as a solvent.
  • Table 1 components constituting the photosensitive resin composition represented by abbreviations (A-1 to F-1) are as shown below.
  • A-2 Methyl ethyl ketone solution of benzyl methacrylate Z methacrylic acid copolymer (mass ratio 85Z15, weight average molecular weight 30000, solid content concentration 40% by mass)
  • A-3 Methyl ethyl ketone solution of copolymer of styrene Z methyl methacrylate Z methacrylic acid (mass ratio 25Z50Z25, weight average molecular weight 55000, solid content concentration 40 mass%).
  • ⁇ -4 Methyl ethyl ketone solution of copolymer of styrene Z methyl methacrylate Z methacrylic acid (mass ratio 25Z50Z25, weight average molecular weight 20000, solid content concentration 40 mass%).
  • ⁇ — 1 Pentaerythritol tetraatrate
  • ⁇ —2 Succinic acid-modified pentaerythritol triatalylate (Aronix TO-756 manufactured by Toa Gosei Co., Ltd.)
  • the photosensitive resin composition is uniformly applied to a polyethylene terephthalate support layer having a thickness of 20 m using a bar coater, and dried in a dryer at 95 ° C. for 3 minutes. Next, a 20-m thick stretched polypropylene protective layer was laminated to the photosensitive resin layer to obtain the photosensitive resin laminates of Examples 1-9.
  • the protective layers of the photosensitive resin laminates of Examples 1 to 9 were peeled off and laminated to a glass substrate. It took about 5 seconds to laminate the photosensitive resin laminate on a 10cm square substrate. Thereafter, the film was exposed at 40 mj / cm 2 with a super high pressure mercury lamp (HMW-801, manufactured by Oak Manufacturing Co., Ltd.) through a glass mask having a 1: 9 line width: space width. At this time, the distance between the support layer and the glass mask was set to 100 m. After peeling off the support layer, 0.05 mass% aqueous solution of potassium hydroxide and potassium hydroxide was sprayed at 23 ° C., and the photopolymerizable resin layer in the unexposed portion was dissolved and removed for development.
  • HMW-801 super high pressure mercury lamp
  • the spraying time at this time was 1.5 times the time (minimum development time) when the photopolymerizable resin layer in the unexposed area was removed with the glass substrate force. Thereafter, post-beta was performed at 240 ° C for 60 minutes to form a black matrix.
  • ⁇ The entire photosensitive resin layer is transferred to the glass substrate.
  • ⁇ Part of the exposed portion of the solid pattern is peeled off together with the support layer, but the matrix pattern is transferred without any problem.
  • the height of the pattern formed on the glass substrate was measured using an alpha step (AS200) manufactured by Tencor Instruments Co., Ltd., and this was defined as the film thickness m).
  • a solid pattern was prepared in the same manner as the above black matrix, and the optical density was measured using a Daletag Macbeth optical densitometer D200-II.
  • a value obtained by dividing the optical density by the above film thickness was obtained, and this was regarded as a light shielding property.
  • the light shielding property was evaluated according to the following rank.
  • the post-beta glass substrate was visually read to see how many step tablet patterns remained. Sensitivity was evaluated according to the following rank
  • the photosensitive ⁇ laminate used in Example 2 and Comparative Example 2 was laminated on a glass substrate, exposed with 4 OmjZcm 2, a value obtained by dividing the developing time at the minimum developing time is 1. close with 1 (minimum developing time Equivalent) and 1.6 (equivalent to over-development) to form a black matrix.
  • the line width of the black matrix corresponding to the mask line width of 20 m was measured with a length measuring microscope.
  • Table 2 Examples 10 and 11 and Comparative Examples 8 and 9. It can be seen that the change in line width of the photosensitive resin laminate of Example 2 is smaller than that of the photosensitive resin laminate of Comparative Example 2.
  • Example 1 D-1: CI Pigment Red 254 and D-3: Pigment Yellow 139 were used in the same manner as in Example 1 instead of carbon black. Make composition solutions 14 and 15.
  • the photosensitive resin composition solutions 14 and 15 were uniformly applied to a polyethylene terephthalate base film having a thickness of 20 m using a bar coater, and the coating was performed in a dryer at 95 ° C. Dry for minutes. Next, a 25 m thick polyethylene protective film is laminated on the resulting photopolymerizable resin composition laminate, and the photosensitive resin laminates of Examples 12 and 13 can be obtained. After peeling off the protective film of the photosensitive resin laminate of Examples 12 and 13 and laminating it on a glass substrate, a pattern with a line width Z space width of 5 ⁇ m / 25 ⁇ m The film is exposed to 40 mjZcm 2 with an ultra-high pressure mercury lamp (HMW-801 manufactured by Oak Manufacturing Co., Ltd.).
  • HMW-801 ultra-high pressure mercury lamp
  • aqueous solution of hydroxyaluminum hydroxide is sprayed at 23 ° C for about 30 seconds to dissolve and remove the unexposed photosensitive resin layer. After that, post-beta at 200 ° C for 15 minutes to form color pixels.
  • the components of the photosensitive resin composition were mixed in the ratios shown in Examples 14 to 17 and Comparative Example 10 in Table 1, and the photosensitive resin composition solution having a solid content of 10% by mass using methyl ethyl ketone as a solvent. 14-17 and the comparative photosensitive resin composition solution 10 were obtained.
  • the photosensitive resin composition solutions 14 to 17 and the comparative photosensitive resin composition solution 10 were uniformly applied to a polyethylene terephthalate support layer having a thickness of 20 m using a bar coater. Dry in a ° C dryer for 3 minutes. Then, a 20 m thick stretched polypropylene protective layer was laminated to the photosensitive resin layer, and the photosensitive resin laminates of Examples 14 to 17 and Comparative Example 10 were obtained.
  • the protective layer of the photosensitive resin laminate of Examples 14 to 17 and Comparative Example 10 was peeled off and laminated to a glass substrate. Thereafter, the support layer was peeled off, and exposed to lOOmjZcm 2 with a super high pressure mercury lamp (HMW-801, manufactured by Oak Manufacturing Co., Ltd.) through a glass mask having a matrix pattern with a line width: space width of 1: 9. At this time, the distance between the photosensitive resin layer and the glass mask was set to 100 / zm.
  • HMW-801 super high pressure mercury lamp
  • Transferability to a glass substrate was evaluated as follows because the support layer was peeled off before exposure of noturn.
  • Comparative photosensitive resin compositions solutions 1 to 7 having a solid content of 10% by weight.
  • This comparative photosensitive resin composition In the same manner as in the Examples, the product solutions 1 to 7 were applied onto a 20 m thick polyethylene terephthalate base film, and a 20 m thick stretched polypropylene protective layer was laminated to the photosensitive films of Comparative Examples 1 to 7. A hydrophilic resin laminate was produced. Using these photosensitive resin laminates of Comparative Examples 1 to 7, a black matrix was formed on a glass substrate in the same manner as in the Examples. Regarding the evaluation, the same items as in the examples were evaluated, and the results are shown in Table 1.
  • the photosensitive resin composition of Comparative Example 4 showed coating unevenness after coating and drying on the base film. Further, the exposed portion where the adhesiveness between the photosensitive resin layer and the support layer in the unexposed portion was high was peeled off from the substrate cover when the support layer was peeled off.
  • the photosensitive resin composition of Comparative Example 5 had a portion with a low optical density as apparent to the eye after application, and could not be applied uniformly.
  • the photosensitive resin composition solution 3 prepared in Example 3 was spin-coated on a 10 cm square glass substrate at 500 rpm using a spin coater (Mikasa Spin Coater 1H-360S). After coating, radial coating unevenness occurred toward the edge of the substrate center. In addition, coating irregularities of about lmm occurred at the edge as well as the substrate. In order to laminate the photosensitive resin layer on the glass substrate, it was necessary to further dry it in an oven at 80 ° C for 10 minutes. Furthermore, as in the case of Example 3, exposure and development were performed to form a black matrix. As a result, a pattern remained on the substrate after development.
  • the present invention can be used in the field of flat panel displays such as liquid crystal displays, organic EL displays, and plasma displays, and color filters used in the above liquid crystal displays and organic EL displays, and is particularly preferably used in the field of liquid crystal displays.
  • flat panel displays such as liquid crystal displays, organic EL displays, and plasma displays, and color filters used in the above liquid crystal displays and organic EL displays, and is particularly preferably used in the field of liquid crystal displays.

Abstract

A photosensitive-resin layered product which, when used in forming a resinous black matrix, is excellent in sensitivity, light-shutting properties, thin-line adhesion, line-width stability in overdevelopment, transferability, and productivity. When used in forming color pixels, the photosensitive-resin layered product has high sensitivity. The photosensitive-resin layered product comprises a support layer and a photosensitive resin layer superposed thereon, wherein the photosensitive resin layer is made of a photosensitive resin composition comprising: 3-40 mass% alkali-soluble polymer represented by the following formula (I); 1-40 mass% specific alkali-soluble polymer; 3-25 mass% photopolymerizable compound having an ethylenically unsaturated double bond; 0.1-20 mass% photopolymerization initiator; and 40-70 mass% coloring pigment, the proportion of the alkali-soluble polymer represented by the formula (I) to the specific alkali-soluble polymer (mass ratio) being from 1:5 to 16:1.

Description

感光性樹脂積層体  Photosensitive resin laminate
技術分野  Technical field
[0001] 本発明は、ブラックマトリックス付き基板、カラー画素付き基板、及びカラーフィルタ の製造に有用な感光性樹脂積層体に関する。  The present invention relates to a photosensitive resin laminate useful for manufacturing a substrate with a black matrix, a substrate with color pixels, and a color filter.
背景技術  Background art
[0002] 液晶ディスプレイには、一般にカラーフィルタと呼ばれるバックライト光を色づけする 部材がある。カラーフィルタは、赤、緑、青のカラー画素とそれらを仕切るブラックマト リックスより構成される。カラー画素はカラー化の為に必要である力 ブラックマトリクス は、 TFTの誤作動防止、コントラストの向上、混色を防ぐなどの目的のためカラー画 素間に格子状に配されるのが通常である。  A liquid crystal display has a member that colors backlight light, generally called a color filter. The color filter is composed of red, green, and blue color pixels and a black matrix that separates them. The power required for colorization of color pixels The black matrix is usually arranged in a grid pattern between the color pixels for the purpose of preventing TFT malfunction, improving contrast, and preventing color mixing. .
[0003] さて、近年液晶ディスプレイにはますますの高品質が求められて 、る。例えば、ディ スプレイの色再現性を高めるためにカラー画素の色純度を上げることが求められて ヽ る。色純度を上げるとバックライト光の透過率が減少し、輝度が下がる。バックライト光 の透過率の減少を補 ヽバックライト光の輝度を上げると、カラー画素とカラー画素とを 仕切るブラックマトリックスがノ ックライト光を遮光しきれず一部の光が透過するように なる。し力も、パネルの輝度を確保するためには開口部すなわちカラー画素部分を 大きく設計する必要があるため、それに対応してブラックマトリックスは細線ィ匕される 傾向にもある。従来ブラックマトリックスはスパッタ法による金属薄膜、例えばクロムに より製造されていた。しかし、環境への悪影響を考慮すると今後のクロムの使用は困 難であり、フォトリソグラフィ一法を用いた黒色顔料を含む樹脂からなるブラックマトリツ タス（以下、榭脂ブラックマトリックス、という）が主流になりつつある。  [0003] In recent years, liquid crystal displays have been required to have higher quality. For example, in order to improve the color reproducibility of the display, it is required to increase the color purity of the color pixel. Increasing the color purity decreases the backlight transmittance and decreases the brightness. Compensating for a decrease in the transmittance of the backlight light When the luminance of the backlight light is increased, the black matrix that separates the color pixels from the color pixels cannot completely block the knock light, and part of the light is transmitted. However, since the aperture, that is, the color pixel portion needs to be designed to be large in order to ensure the brightness of the panel, the black matrix tends to be thinned accordingly. Conventionally, the black matrix has been manufactured by a metal thin film formed by sputtering, for example, chromium. However, considering the negative impact on the environment, it is difficult to use chromium in the future, and black matrix (hereinafter referred to as “resin black matrix”) made of a resin containing a black pigment using a photolithography method is the mainstream. It is becoming.
[0004] さらに、液晶ディスプレイの製造には生産性の向上が求められており、カラーフィル タも例外ではない。たとえば、液晶ディスプレイの大型化に伴いカラーフィルタ基板の 露光面積も広がるが、露光マスクを基板と同じ大きさとする事は難しい。そのため、一 枚のカラーフィルタ基板を分割して繰り返し露光することになる。そうすると一回あたり の露光時間は生産性に大きく影響し、高感度のフォトリソグラフィー材料が求められる ようになる。さらに、塗布、乾燥、露光、現像といったフォトリソグラフィー工程自体の簡 略化も重要な生産性向上の手段と考えられている。 [0004] Further, in the manufacture of liquid crystal displays, improvement in productivity is required, and color filters are no exception. For example, the exposure area of the color filter substrate increases as the liquid crystal display becomes larger, but it is difficult to make the exposure mask the same size as the substrate. Therefore, a single color filter substrate is divided and repeatedly exposed. As a result, the exposure time per time greatly affects productivity, and high-sensitivity photolithography materials are required. It becomes like this. In addition, simplification of the photolithography process itself such as coating, drying, exposure, and development is considered as an important productivity improvement means.
[0005] 特に榭脂ブラックマトリックスは、遮光性が高いことが本来の機能であるため、感光 性榭脂によって製造する場合感度を上げることが非常に難しい。また、遮光性が高く 底面には表面に比して少量の光しか届かないため、密着性、とりわけ細線の密着性 、および過現像時の線幅安定性を確保することが非常に難しい。同様に、カラー画 素もブラックマトリックスほどではないが着色顔料が露光波長に吸収を持っため感度 が著しく低下する。  [0005] In particular, since the essential function of the rosin black matrix is that it has a high light-shielding property, it is very difficult to increase the sensitivity when it is produced using a photosensitive rosin. In addition, since the light shielding property is high and only a small amount of light reaches the bottom surface as compared with the surface, it is very difficult to ensure adhesion, particularly fine line adhesion, and line width stability during overdevelopment. Similarly, although the color pixels are not as large as the black matrix, the sensitivity of the color pigments is significantly reduced because the colored pigments absorb at the exposure wavelength.
[0006] このような課題に鑑み、いくつかの先行技術が開示されている。例えば、特許文献 1 には、光学濃度が高く良好なブラックマトリックスパターンが得られる光重合性黒色組 成物が開示されている。また、特許文献 2には、特定の光重合性榭脂組成物を支持 フィルムに積層したカラーフィルタ形成用材料が開示されている。しカゝしながら、いず れにおいても、十分な感度、遮光性、細線密着性、過現像時の線幅安定性を有し、 かつ生産性をも同時に満足させるような榭脂ブラックマトリックス形成材料の開示はな かった。  [0006] In view of such problems, several prior arts have been disclosed. For example, Patent Document 1 discloses a photopolymerizable black composition capable of obtaining a good black matrix pattern having a high optical density. Patent Document 2 discloses a color filter forming material in which a specific photopolymerizable resin composition is laminated on a support film. However, in any case, a resin black matrix is formed that has sufficient sensitivity, light-shielding properties, fine wire adhesion, line width stability during over-development, and simultaneously satisfies productivity. There was no disclosure of materials.
特許文献 1：特開 2004— 69754号公報  Patent Document 1: Japanese Patent Application Laid-Open No. 2004-69754
特許文献 2：特開 2005 - 208480号公報  Patent Document 2: Japanese Patent Laid-Open No. 2005-208480
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0007] 本発明は、榭脂ブラックマトリックスを形成するにあたって、感度、遮光性、細線密 着性、過現像時の線幅安定性、転写性、生産性に優れた感光性榭脂積層体を提供 すること、ならびにそれを用いた榭脂ブラックマトリックスの製造方法を提供することを 目的とする。さら〖こ、カラー画素を形成するにあたって、高感度な感光性榭脂積層体 を提供すること、ならびにそれを用いたカラー画素の製造方法を提供することを目的 とする。 [0007] The present invention provides a photosensitive resin laminate excellent in sensitivity, light shielding property, fine wire adhesion, line width stability during over-development, transferability, and productivity in forming a resin black matrix. It is an object of the present invention to provide a method and a method for producing a black resin black matrix using the same. Furthermore, an object of the present invention is to provide a highly sensitive photosensitive resin laminate and a method for producing a color pixel using the same in forming color pixels.
課題を解決するための手段  Means for solving the problem
[0008] 上記課題を解決するために鋭意研究を重ねた結果、本発明をなすに至った。 [0008] As a result of intensive studies to solve the above problems, the present invention has been made.
[0009] すなわち、本発明は以下のとおりである。 (1)少なくとも支持層と感光性榭脂層とを積層してなり、該感光性榭脂層が、 下記式 (I)で表されるアルカリ可溶性高分子 3〜40質量％、 That is, the present invention is as follows. (1) At least a support layer and a photosensitive resin layer are laminated, and the photosensitive resin layer is 3 to 40% by mass of an alkali-soluble polymer represented by the following formula (I),
重量平均分子量が 3, 000〜100, 000であるメタクリル酸べンジル又はアクリル酸べ ンジルを共重合したアルカリ可溶性高分子及び重量平均分子量が 3, 000-50, 00 0であるアクリル系のアルカリ可溶性高分子力もなる群より選ばれる少なくとも一種の アルカリ可溶性高分子 1〜40質量％、  Alkali-soluble polymer copolymerized with benzyl methacrylate or benzyl acrylate with a weight average molecular weight of 3,000 to 100,000 and acrylic alkali-soluble with a weight average molecular weight of 3,000-50,000 1 to 40% by mass of at least one alkali-soluble polymer selected from the group consisting of polymer strength,
エチレン性不飽和二重結合を有する光重合性化合物 3〜25質量％、  3-25% by mass of a photopolymerizable compound having an ethylenically unsaturated double bond,
光重合開始剤 0. 1〜20質量％、  Photopolymerization initiator 0.1 to 20% by mass,
着色顔料 40〜70質量％を含み、かつ、  Containing 40 to 70% by weight of a color pigment, and
該式 (I)で表されるアルカリ可溶性高分子:該重量平均分子量が 3, 000〜： L00, 00 0であるメタクリル酸べンジル又はアクリル酸ベンジルを共重合したアルカリ可溶性高 分子及び重量平均分子量が 3, 000〜50, 000であるアクリル系のアルカリ可溶性 高分子力 なる群より選ばれる少なくとも一種のアルカリ可溶性高分子 (質量比） = 1 : 5〜16： 1  Alkali-soluble polymer represented by formula (I): Alkali-soluble polymer and weight-average molecular weight copolymerized with benzyl methacrylate or benzyl acrylate having a weight-average molecular weight of 3,000-: L00,000 Acrylic alkali-soluble polymer having a molecular weight of 3,000 to 50,000 at least one alkali-soluble polymer (mass ratio) selected from the group consisting of: 1: 5 to 16: 1
である感光性榭脂組成物からなる感光性榭脂積層体。  A photosensitive resin laminate comprising a photosensitive resin composition.
[0010] [化 1] [0010] [Chemical 1]
COOHCOOH
HOOC-Y-CO-0- X-0-CO— Z— CO-0+-X— 0-CO— Y-COOH ( I ) HOOC-Y-CO-0- X-0-CO— Z— CO-0 + -X— 0-CO— Y-COOH (I)
COOH  COOH
n  n
[0011] (式 (I)中、 Xは下記式 (Π)で表される基、 Yはジカルボン酸無水物の酸無水物基を 除いた残基、 Zはテトラカルボン酸二無水物の酸無水物基を除いた残基、 nは 1〜20 の整数である。下記式 (Π)中の Rおよび Rはそれぞれ互いに独立な Hまたは CH (In the formula (I), X is a group represented by the following formula (下 記), Y is a residue excluding an acid anhydride group of dicarboxylic anhydride, Z is an acid of tetracarboxylic dianhydride. Residue excluding an anhydride group, n is an integer of 1 to 20. In the following formula (Π), R and R are each independently H or CH
1 2 3 基を表す。 )  1 2 3 represents a group. )
[0012] [化 2] [0012] [Chemical 2]
Figure imgf000005_0001
(2)該感光性榭脂層が、
Figure imgf000005_0001
(2) The photosensitive resin layer is
上記式 (I)で表されるアルカリ可溶性高分子 3〜40質量％、 3-40% by mass of the alkali-soluble polymer represented by the above formula (I),
重量平均分子量が 3, 000〜100, 000であるメタクリル酸べンジル又はアクリル酸べ ンジルを共重合したアル力リ可溶性高分子 1〜40質量％、 1 to 40% by mass of an alcoholic soluble polymer copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000,
エチレン性不飽和二重結合を有する光重合性化合物 3〜25質量％、 3-25% by mass of a photopolymerizable compound having an ethylenically unsaturated double bond,
光重合開始剤 0. 1〜20質量％、 Photopolymerization initiator 0.1 to 20% by mass,
着色顔料 40〜70質量％を含み、かつ、 Containing 40 to 70% by weight of a color pigment, and
該式 (I)で表されるアルカリ可溶性高分子:該重量平均分子量が 3, 000〜： L00, 00 0であるメタクリル酸べンジル又はアクリル酸ベンジルを共重合したアルカリ可溶性高 分子 (質量比） = 1 : 5〜16 : 1 Alkali-soluble polymer represented by formula (I): Alkali-soluble polymer (mass ratio) obtained by copolymerization of benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to L0,000 = 1: 5 to 16: 1
である感光性榭脂組成物からなる（1)記載の感光性榭脂積層体。 The photosensitive resin laminate according to (1), comprising the photosensitive resin composition.
(3)該感光性樹脂層が、  (3) The photosensitive resin layer is
上記式 (I)で表されるアルカリ可溶性高分子 3〜40質量％、 3-40% by mass of the alkali-soluble polymer represented by the above formula (I),
重量平均分子量が 3, 000〜50, 000であるメタクリル酸べンジル又はアクリル酸べ ンジルを共重合したアルカリ可溶性高分子 5〜40質量％、 5-40% by mass of an alkali-soluble polymer copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 50,000,
エチレン性不飽和二重結合を有する光重合性化合物 5〜25質量％、 5-25% by mass of a photopolymerizable compound having an ethylenically unsaturated double bond,
光重合開始剤 0. 1〜20質量％、 Photopolymerization initiator 0.1 to 20% by mass,
着色顔料 40〜70質量％を含み、かつ、 Containing 40 to 70% by weight of a color pigment, and
該式 (I)で表されるアルカリ可溶性高分子:該重量平均分子量が 3, 000〜50, 000 であるメタクリル酸べンジル又はアクリル酸ベンジルを共重合したアルカリ可溶性高 分子 (質量比） = 1： 5〜5： 1である（2)記載の感光性榭脂積層体。 Alkali-soluble polymer represented by the formula (I): alkali-soluble polymer (mass ratio) = 1 copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 50,000 : The photosensitive resin laminate according to (2), which is 5 to 5: 1.
(4)該式 (I)で表されるアルカリ可溶性高分子：該重量平均分子量が 3, 000〜： L00, 000であるメタクリル酸べンジル又はアクリル酸ベンジルを共重合したアルカリ可溶性 高分子及び重量平均分子量が 3, 000〜50, 000であるアクリル系のアルカリ可溶 性高分子力 なる群より選ばれる少なくとも一種のアルカリ可溶性高分子 (質量比） = 2： 1〜16： 1である（1)記載の感光性榭脂積層体。 (4) Alkali-soluble polymer represented by the formula (I): Alkali-soluble by copolymerization of benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to L00,000 Polymer and weight average molecular weight of 3,000 to 50,000 acrylic alkali-soluble polymer at least one kind selected from the group consisting of alkali-soluble polymer (mass ratio) = 2: 1 to 16: 1 (1) The photosensitive resin laminate according to (1).
(5)感光性榭脂組成物中に、光重合開始剤としてォキシムエステルイ匕合物を含む（ 1 )〜 (4)の 、ずれか一項に記載の感光性榭脂積層体。  (5) The photosensitive resin laminate according to any one of (1) to (4), wherein the photosensitive resin composition contains an oxime ester compound as a photopolymerization initiator.
(6)感光性榭脂組成物中に、エチレン性不飽和二重結合を有する光重合性ィ匕合物 として下記式 (III)で表される化合物を含む（1)〜 (4)の 、ずれか一項に記載の感光 性樹脂積層体。  (6) The photosensitive resin composition contains a compound represented by the following formula (III) as a photopolymerizable compound having an ethylenically unsaturated double bond: (1) to (4) The photosensitive resin laminate according to any one of the preceding items.
[0014] [化 3]  [0014] [Chemical 3]
Figure imgf000006_0001
Figure imgf000006_0001
[0015] (式 (ΠΙ)中、 R、 Rおよび Rは、それぞれ互いに独立な Hまたは CH基を表す。 R (In the formula (ΠΙ), R, R and R each independently represent an H or CH group. R
3 4 5 3 6 は 2価の連結基で、炭素数 2〜8のアルキレン基、炭素数 3〜 10のシクロアルキレン 基、及び炭素数 6〜10のフエ-レン基力もなる群より選ばれる一種の基を表す。 ) 3 4 5 3 6 is a divalent linking group selected from the group consisting of an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, and a phenyl group having 6 to 10 carbon atoms. Represents a group of )
(7)着色顔料が黒色顔料である（1)に記載の感光性榭脂積層体。 (7) The photosensitive resin laminate according to (1), wherein the color pigment is a black pigment.
(8) (1)〜 (4)のいずれか一項に記載の感光性榭脂積層体を、少なくとも、基板にラ ミネートする工程、露光する工程、現像する工程を順に含むカラー画素付き基板の 製造方法。  (8) A substrate with a color pixel comprising the photosensitive resin laminate according to any one of (1) to (4) in the order of at least a step of laminating a substrate, a step of exposing, and a step of developing. Production method.
(9) (7)に記載の感光性榭脂積層体を、少なくとも、基板にラミネートする工程、露光 する工程、支持層を剥離する工程、現像する工程を順に含むブラックマトリックス付き 基板の製造方法。  (9) A method for producing a substrate with a black matrix, comprising at least a step of laminating the photosensitive resin laminate according to (7) on a substrate, an exposing step, a step of peeling a support layer, and a developing step.
(10) (7)に記載の感光性榭脂積層体を、少なくとも、基板にラミネートする工程、支 持層を剥離する工程、露光する工程、現像する工程を順に含むブラックマトリックス 付き基板の製造方法。 (10) A black matrix comprising, in order, at least the step of laminating the photosensitive resin laminate according to (7) on a substrate, the step of peeling the support layer, the step of exposing, and the step of developing. A method for manufacturing a substrate with a substrate.
(11)少なくとも、（9)又は（10)に記載の方法で基板上にブラックマトリックスを形成 する工程、該ガラス基板上のブラックマトリックスで覆われて ヽな 、部分の少なくとも 一部に感熱性または感光性のカラーインクをインクジェット方式により印刷する印刷 工程を順に含むカラーフィルタの製造方法。  (11) At least a step of forming a black matrix on the substrate by the method according to (9) or (10), covered with the black matrix on the glass substrate, A method for producing a color filter, which includes a printing step of printing photosensitive color ink by an ink jet method.
(12) (11)記載の方法により製造されるカラーフィルタ。  (12) A color filter produced by the method according to (11).
発明の効果  The invention's effect
[0016] 本発明の感光性榭脂積層体は、榭脂ブラックマトリックスを形成するにあたって、感 度、遮光性、細線密着性、過現像時の線幅安定性、転写性、生産性に優れるという 効果を奏する。また、本発明の感光性榭脂積層体は、カラー画素を形成するにあた つて非常に感度が高 、と 、う効果を奏する。  The photosensitive resin laminate of the present invention is excellent in sensitivity, light-shielding property, fine wire adhesion, line width stability during over-development, transferability, and productivity when forming a resin black matrix. There is an effect. In addition, the photosensitive resin laminate of the present invention has the effect of being very sensitive in forming color pixels.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0017] 以下、本発明について具体的に説明する。なお、本発明の感光性榭脂積層体中 の感光性榭脂層は感光性榭脂組成物からなる。感光性榭脂組成物の各成分の配合 量について記載する場合は、感光性榭脂組成物中の固形分全体を 100%とした場 合の質量％で記載される。 [0017] The present invention will be specifically described below. The photosensitive resin layer in the photosensitive resin laminate of the present invention comprises a photosensitive resin composition. When describing the blending amount of each component of the photosensitive resin composition, it is described in mass% when the total solid content in the photosensitive resin composition is 100%.
[0018] 本発明の感光性榭脂積層体は、感光性榭脂組成物中に下記式 (I)で表されるアル カリ可溶性高分子 (以下、単に化合物ということがある。）を 3〜40質量％含有する。 含有量は、感度、密着性、線幅再現性の観点から 3質量％以上であり、支持層から 基材への転写性の観点から 40質量％以下である。転写性とは本発明の感光性榭脂 積層体を基材にラミネートし、露光する前もしくは露光した後支持層を剥離するに際 して、感光性榭脂層が基材へ転写される性能を言う。転写性が十分ではない場合、 支持層を剥離する際に未露光部もしくは露光部分が支持層とともに基板力も剥離し てしまう。その含有量は 5〜30質量％が好ましぐ 8〜25質量％がより好ましぐ 8〜2 0質量％がさらに好ましい。  [0018] The photosensitive resin laminate of the present invention comprises an alkali-soluble polymer represented by the following formula (I) (hereinafter sometimes simply referred to as a compound) 3 to 3 in the photosensitive resin composition. Contains 40% by mass. The content is 3% by mass or more from the viewpoint of sensitivity, adhesion, and line width reproducibility, and 40% by mass or less from the viewpoint of transferability from the support layer to the substrate. Transferability refers to the ability of the photosensitive resin layer of the present invention to be laminated to a substrate, and the photosensitive resin layer transferred to the substrate when the support layer is peeled off before or after exposure. Say. When the transferability is not sufficient, when the support layer is peeled off, the unexposed part or the exposed part peels off the substrate force together with the support layer. The content is preferably 5 to 30% by mass, more preferably 8 to 25% by mass, and still more preferably 8 to 20% by mass.
[0019] [化 4] COOH [0019] [Chemical 4] COOH
HOOC-Y-CO-O- X_0-CO— Z— CO-0+-X— O-CO— Y-COOH ( I ) HOOC-Y-CO-O- X_0-CO— Z— CO-0 + -X— O-CO— Y-COOH (I)
COOH COOH
n  n
[0020] (式 (I)中、 Xは下記式 (Π)で表される基、 Yはジカルボン酸無水物の酸無水物基を 除いた残基、 Zはテトラカルボン酸二無水物の酸無水物基を除いた残基、 nは 1〜20 の整数である。下記式 (Π)中の Rおよび Rはそれぞれ互いに独立な Hまたは CH [0020] (In the formula (I), X is a group represented by the following formula (Π), Y is a residue excluding the acid anhydride group of dicarboxylic anhydride, Z is an acid of tetracarboxylic dianhydride. Residue excluding an anhydride group, n is an integer of 1 to 20. In the following formula (Π), R and R are each independently H or CH
1 2 3 基を表す。 )  1 2 3 represents a group. )
[0021] [化 5]  [0021] [Chemical 5]
Figure imgf000008_0001
Figure imgf000008_0001
[0022] ここで、「酸無水物基」とは、「一 CO— O— CO—基」を言う。 Here, the “acid anhydride group” refers to “one CO—O—CO— group”.
[0023] また、ジカルボン酸無水物としては、例えば無水マレイン酸、無水コハク酸、無水ィ タコン酸、無水フタル酸、無水テトラヒドロフタル酸、無水へキサヒドロフタル酸、無水 メチルエンドメチレンテトラヒドロフタル酸、無水クロレンド酸、メチルテトラヒドロ無水フ タル酸、無水ダルタル酸などが挙げられる。 [0023] Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, Examples include chlorendic anhydride, methyltetrahydrophthalic anhydride, and dartaric anhydride.
[0024] また、テトラカルボン酸二無水物としては、例えば無水ピロメリット酸、ベンゾフエノン テトラカルボン酸二無水物、ビフエ-ルテトラカルボン酸二無水物、ビフエ-ルエーテ ルテトラカルボン酸二無水物等の芳香族多価カルボン酸無水物が挙げられる。  [0024] Further, examples of the tetracarboxylic dianhydride include pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride and the like. An aromatic polyhydric carboxylic acid anhydride is mentioned.
[0025] 本発明に用いられる上記式 (I)で表される化合物は、例えば、特開 2001— 35473 5号公報に記載の方法により得ることができる。上記式 (I)で表される化合物は重合 鎖内にジカルボン酸無水物残基を実質上有しておらず、その末端に有している。そ のため、重合鎖内にジカルボン酸無水物残基を有する化合物とは異なり、同じ固形 分濃度でも、溶液粘度を制御し易ぐ塗布時の作業性の改善、コーティング特性の向 上、膜厚の均一化を図ることができる。 [0025] The compound represented by the above formula (I) used in the present invention can be obtained, for example, by the method described in JP-A No. 2001-354735. The compound represented by the above formula (I) has substantially no dicarboxylic acid anhydride residue in the polymerization chain, but has at its end. Therefore, unlike a compound having a dicarboxylic acid anhydride residue in the polymer chain, even at the same solid content concentration, the solution viscosity can be easily controlled to improve workability during coating and improve coating properties. In addition, the film thickness can be made uniform.
[0026] 本発明に用いられる上記式 (I)で表される化合物は、付加重合可能なエチレン性 不飽和二重結合をィ匕合物中に少なくとも二つ有する。この化合物を含む感光性榭脂 組成物は、光重合開始剤を活性化させる所定波長の光線の照射を受けたとき、光学 濃度が高くても、光重合開始剤の作用により付加重合して硬化することができる。こ のため、表示コントラストが高ぐ R、 G、 Bの発色の美しいカラーフィルタを製造するこ とができる。特にこの効果は、ブラックマトリックス形成にこの化合物を用いた場合、遮 光性と感度の関係において顕著となる。後述の実施例に示すとおり、黒色顔料の添 加量を増やして遮光性を上げた場合、通常、遮光性が上がるとともに感度が低下す る力 上記式 (I)で表される化合物を用いた場合は感度低下が低く抑えられる。  [0026] The compound represented by the above formula (I) used in the present invention has at least two ethylenically unsaturated double bonds capable of addition polymerization in the compound. The photosensitive resin composition containing this compound is cured by addition polymerization by the action of the photopolymerization initiator even when the optical density is high when irradiated with light of a predetermined wavelength that activates the photopolymerization initiator. can do. This makes it possible to produce color filters with high R, G, and B colors with high display contrast. In particular, when this compound is used for forming a black matrix, this effect is remarkable in the relationship between light shielding properties and sensitivity. As shown in the examples below, when the amount of black pigment added is increased to increase the light shielding property, the compound represented by the above formula (I) is usually used to increase the light shielding property and reduce the sensitivity. In this case, the sensitivity reduction can be kept low.
[0027] 本発明の感光性榭脂積層体は、感光性榭脂組成物中に重量平均分子量が 3, 00 0〜： LOO, 000であるメタクリル酸べンジル又はアクリル酸ベンジルを共重合したアル カリ可溶性高分子及び重量平均分子量が 3, 000-50, 000であるアクリル系のァ ルカリ可溶性高分子力 なる群より選ばれる少なくとも一種のアルカリ可溶性高分子 を 1〜40質量％含有する。一般に、黒色顔料として広く用いられるカーボンブラック は表面積が大きぐ顔料分散した感光性榭脂組成物に用いると、チキソトロピー性に 富んだ流動性の悪い液体になりやすい。遮光性を向上させるにはこのような黒色顔 料を多く配合させる必要があるが、基板に直接塗布する製法では塗布均一性を確保 するのが難 、 (谷口彰敏、「カラーフィルタ最新技術動向〜構成材料'製造 '評価. 海外動向〜」、第 1刷、株式会社 情報機構、 2005年 5月 31日、 p81— 101)。一方 、本発明においては、パターユング特性に優れる上記式 (I)で表される化合物と顔料 分散や塗布安定性や転写性に優れる上記アルカリ可溶性高分子とをともに配合して 感光性榭脂組成物とし、更に感光性榭脂積層体とすることで、簡単に遮光性の高い 均一な感光性榭脂層を基板上に積層することができる。  [0027] The photosensitive resin laminate of the present invention is obtained by copolymerizing benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to LOO, 000 in a photosensitive resin composition. 1 to 40% by mass of a potassium soluble polymer and at least one alkali-soluble polymer selected from the group consisting of acrylic alkaline soluble polymers having a weight average molecular weight of 3,000 to 50,000. Generally, carbon black, which is widely used as a black pigment, tends to be a liquid with poor thirotropic properties and poor fluidity when used in a photosensitive resin composition having a large surface area and dispersed in a pigment. In order to improve the light-shielding properties, it is necessary to add a lot of such black pigment, but it is difficult to ensure coating uniformity with the manufacturing method that applies directly to the substrate. Composition material 'Manufacturing' evaluation. Overseas trend ~ ", 1st edition, Information Organization Co., Ltd., May 31, 2005, p81-101). On the other hand, in the present invention, the compound represented by the above formula (I) having excellent patterning characteristics and the alkali-soluble polymer having excellent pigment dispersion, coating stability, and transferability are blended together. Further, by forming a photosensitive resin laminate, a uniform photosensitive resin layer having a high light shielding property can be easily laminated on the substrate.
[0028] 本発明の感光性榭脂積層体は、感光性榭脂組成物中に、重量平均分子量が 3, 0 00〜： L00, 000であるメタクリル酸べンジル又はアクリル酸ベンジルを共重合したァ ルカリ可溶性高分子及び重量平均分子量が 3, 000〜50, 000であるアクリル系の アルカリ可溶性高分子カゝらなる群より選ばれる少なくとも一種のアルカリ可溶性高分 子を 1〜40質量％含有する。 [0028] The photosensitive resin laminate of the present invention is obtained by copolymerizing benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 300,000 to L00, 000 in the photosensitive resin composition. Alkali-soluble polymer and at least one alkali-soluble polymer selected from the group consisting of acrylic alkali-soluble polymers having a weight average molecular weight of 3,000 to 50,000 Contains 1-40% by weight of the child.
[0029] 重量平均分子量が 3, 000〜100, 000である（メタ）アクリル酸ベンジルを共重合し たアルカリ可溶性高分子について説明する。ここで、（メタ）アクリルとは、メタアクリル 及びアクリルを表す。以下同様である。  [0029] An alkali-soluble polymer obtained by copolymerizing benzyl (meth) acrylate having a weight average molecular weight of 3,000 to 100,000 will be described. Here, (meth) acryl represents methacryl and acryl. The same applies hereinafter.
[0030] (メタ)アクリル酸ベンジルを共重合したアルカリ可溶性高分子の含有量は、 1〜4 0質量％である。含有量は、 5〜40質量％であることがより好ましい。含有量は、支持 層から基材への転写性及びラミネート性の観点から、 5質量％以上がより好ましぐ感 度、密着性及び線幅安定性の観点力も 40質量％以下がより好ましい。その含有量 は 8〜30質量％がより好ましぐ 10〜25質量％がより好ましぐ 10〜18質量％が最 も好ましい。  [0030] The content of the alkali-soluble polymer copolymerized with benzyl (meth) acrylate is 1 to 40% by mass. The content is more preferably 5 to 40% by mass. From the viewpoints of transferability from the support layer to the base material and lamination, the content is more preferably 5% by mass or more, and the viewpoint power of adhesiveness and line width stability is more preferably 40% by mass or less. The content is preferably 8-30% by mass, more preferably 10-25% by mass, and most preferably 10-18% by mass.
[0031] (メタ）アクリル酸ベンジルを共重合したアルカリ可溶性高分子中には (メタ)アクリル 酸ベンジルを 50〜95質量％共重合することが好まし!/、。 （メタ）アクリル酸ベンジルの 共重合の割合は、黒色顔料の分散性、現像残渣、ラミネート性の観点から、 50質量 %以上が好ましぐ現像速度の観点から 90質量％以下が好ましい。（メタ)アクリル酸 ベンジル共重合の割合は、 60〜90質量％がより好ましぐ 70〜90質量％がさらに 好ましい。  [0031] It is preferable to copolymerize 50 to 95% by mass of benzyl (meth) acrylate in the alkali-soluble polymer copolymerized with benzyl (meth) acrylate! /. The copolymerization ratio of benzyl (meth) acrylate is preferably 90% by mass or less from the viewpoint of development speed, which is preferably 50% by mass or more, from the viewpoint of dispersibility of black pigment, development residue, and laminating property. (Meth) acrylic acid The proportion of benzyl copolymerization is more preferably from 60 to 90 mass%, more preferably from 70 to 90 mass%.
[0032] (メタ）アクリル酸ベンジルを共重合したアルカリ可溶性高分子は、側鎖にカルボキ シル基又はカルボン酸無水物基を有する単量体を共重合して 、ることが好まし 、。 側鎖にカルボキシル基又はカルボン酸無水物基を有する単量体とは、例えば、（メタ )アクリル酸、フマル酸、ケィ皮酸、クロトン酸、ィタコン酸、シトラコン酸、マレイン酸無 水物、マレイン酸半エステル等が挙げられる。側鎖にカルボキシル基を有する単量 体を共重合する割合は、現像性の観点力 5質量％以上が好ましぐ黒色顔料の分 散性、現像後に黒色顔料が基板へ付着するのを抑制する観点から、 30質量％以下 が好まし!/、。それを 5〜20質量％共重合することがより好ま U、。  [0032] The alkali-soluble polymer obtained by copolymerizing benzyl (meth) acrylate is preferably copolymerized with a monomer having a carboxyl group or a carboxylic anhydride group in the side chain. Monomers having a carboxyl group or a carboxylic acid anhydride group in the side chain include, for example, (meth) acrylic acid, fumaric acid, cinnamate, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic Examples include acid half esters. The copolymerization ratio of the monomer having a carboxyl group in the side chain is the dispersibility of the black pigment, which is preferably 5% by mass or more from the viewpoint of developability, and suppresses the black pigment from adhering to the substrate after development. From the viewpoint, 30% by mass or less is preferred! It is more preferable to copolymerize 5-20% by weight of U.
[0033] (メタ）アクリル酸ベンジルを共重合したアルカリ可溶性高分子は、その他の単量体 を共重合することもできる。アルキル (メタ)アタリレート、例えば、メチル (メタ)アタリレ ート、ェチル (メタ）アタリレート、 n—ブチル (メタ）アタリレート、 iso—ブチル (メタ）ァク リレート、 sec—ブチル（メタ）アタリレート、 tert—ブチル（メタ）アタリレート、 2—ェチル へキシル (メタ）アタリレート、 [0033] The alkali-soluble polymer obtained by copolymerizing benzyl (meth) acrylate can also be copolymerized with other monomers. Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate Tert-Butyl (meth) acrylate, 2-ethyl Hexyl (meth) atarylate,
ヒドロキシル基を有する (メタ)アタリレート、例えば、 2—ヒドロキシェチル (メタ)アタリレ ート、 2—ヒドロキシプロピル（メタ）アタリレート、グリセロールモノ（メタ）アタリレート、 シクロアルキル基を有する（メタ）アタリレート、例えば、シクロへキシル (メタ）アタリレー ト、イソボル-ル (メタ）アタリレート、ジシクロペンタ-ル (メタ）アタリレート、ジシクロべ ンタジェ-ル (メタ）アタリレート、ァダマンチル (メタ）アタリレート、 その他、例えば、（メタ)アクリルアミド、（メタ)アクリロニトリル、フエ-ル (メタ）アタリレ ート、グリシジルメタタリレート、スチレンが挙げられる。特に、 2—ヒドロキシェチル (メ タ）アタリレートまたは 2—ヒドロキシプロピル (メタ）アタリレートが好ましい。その他の単 量体の、アルカリ可溶性高分子中の共重合の割合は、 5〜30質量％が好ましい。特 に、その他の単量体として 2—ヒドロキシェチル (メタ）アタリレートまたは 2—ヒドロキシ プロピル (メタ)アタリレートを用いる場合の共重合の割合は、黒色顔料の分散性、ラミ ネート性の観点から 5質量％以上が好ましぐ耐熱性、耐薬品性の観点力も 30質量 %以下が好ましい。共重合の割合は、 5〜15質量％とすることがより好ましい。  (Meth) acrylate having a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, (meth) having a cycloalkyl group Atalylates, such as cyclohexyl (meth) atrelate, isobornyl (meth) atalylate, dicyclopentatal (meth) atarylate, dicyclopentagel (meth) atarylate, adamantyl (meth) atalylate, Other examples include (meth) acrylamide, (meth) acrylonitrile, phenol (meth) acrylate, glycidyl methacrylate, and styrene. In particular, 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate is preferred. The copolymerization ratio of the other monomer in the alkali-soluble polymer is preferably 5 to 30% by mass. In particular, when 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate is used as the other monomer, the copolymerization ratio depends on the dispersibility and lamination of the black pigment. From the viewpoint of heat resistance and chemical resistance, 5% by mass or more is preferable, and 30% by mass or less is preferable. The copolymerization ratio is more preferably 5 to 15% by mass.
[0034] (メタ）アクリル酸ベンジルを共重合したアルカリ可溶性高分子は、その重量平均分 子量が 3, 000-50, 000であることがより好ましい。現像性の観点力 分子量は 50 , 000以下がより好ましぐ密着性の観点から 3, 000以上がより好ましい。その重量 平均分子量力 s 10, 000〜40, 000であること力更に好まし!/、。 [0034] The weight average molecular weight of the alkali-soluble polymer copolymerized with benzyl (meth) acrylate is more preferably 3,000-50,000. From the viewpoint of adhesion, the molecular weight is more preferably not less than 3,000, more preferably not less than 3,000. Its weight average molecular weight force s 10,000 to 40,000 is more preferred power /!
[0035] 分子量の測定は、 日本分光 (株)製ゲルパーミエーシヨンクロマトグラフィー（GPC)  [0035] The molecular weight was measured by Gel Permeation Chromatography (GPC) manufactured by JASCO Corporation.
(ポンプ: Gulliver, PU— 1580型、カラム：昭和電工 (株)製 Shodex (登録商標）（K F— 807、 KF— 806M、 KF— 806M、 KF— 802. 5) 4本直列、移動層溶媒：テ卜ラ ヒドロフラン、ポリスチレン標準サンプル（昭和電工 (株）製 Shodex STANDARD SM- 105)による検量線使用）により重量平均分子量 (ポリスチレン換算）として求め られる。  (Pump: Gulliver, PU—1580 type, Column: Shodex (registered trademark) manufactured by Showa Denko K.K. (KF—807, KF—806M, KF—806M, KF—802.5) 4 in series, moving bed solvent: It is determined as the weight average molecular weight (polystyrene equivalent) by using tetrahydrofuran and polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK).
[0036] (メタ）アクリル酸ベンジルを共重合したアルカリ可溶性高分子は、カルボキシル基 の量が酸当量で 200〜2, 000であることが好ましい。酸当量とは、 1当量のカルボキ シル基を有する線状重合体の質量を示す。現像性の観点から酸当量は 2, 000以下 が好ましぐ現像後に黒色顔料が基板へ付着するのを抑制する観点から、酸当量は 200以上力好まし!/ヽ。その酸当量 ίま 400〜900力より好ましく、 500〜800力 ^さらに 好ましい。なお、酸当量の測定は、平沼産業 (株)製平沼自動滴定装置 (COM— 55 5)を使用し、 0. ImolZLの水酸ィ匕ナトリウムを用いて電位差滴定法により測定され る。 [0036] The alkali-soluble polymer obtained by copolymerizing benzyl (meth) acrylate preferably has a carboxyl group content of 200 to 2,000 in terms of acid equivalent. The acid equivalent refers to the mass of a linear polymer having 1 equivalent of a carboxyl group. From the viewpoint of developability, the acid equivalent is preferably 2,000 or less. From the viewpoint of suppressing the black pigment from adhering to the substrate after development, the acid equivalent is More than 200 power! / ヽ. Its acid equivalent is more preferably 400 to 900 force, more preferably 500 to 800 force. The acid equivalent is measured by the potentiometric titration method using Hiranuma Automatic Titration System (COM-55 5) manufactured by Hiranuma Sangyo Co., Ltd. and 0.1 mol ImolZL sodium hydroxide.
[0037] (メタ）アクリル酸ベンジルを共重合したアルカリ可溶性高分子は、上記種々単量体 の混合物を、アセトン、メチルェチルケトン、イソプロパノ—ル等の溶剤で希釈した溶 液に、過酸化べンゾィル、ァゾビスイソブチ口-トリル等のラジカル重合開始剤を適量 添加し、過熱攪拌することにより合成を行うことが好ましい。混合物の一部を反応液に 滴下しながら合成を行う場合もある。反応終了後、さらに溶媒を加えて、所望の濃度 に調整する場合もある。合成手段としては、溶液重合以外に、塊状重合、懸濁重合 及び乳化重合を用いて 、もよ 、。  [0037] The alkali-soluble polymer copolymerized with benzyl (meth) acrylate is peroxidized into a solution obtained by diluting a mixture of the above-mentioned various monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to carry out the synthesis by adding an appropriate amount of a radical polymerization initiator such as benzoyl, azobisisobutyric-tolyl and the like, followed by superheated stirring. In some cases, a part of the mixture is added dropwise to the reaction solution. After the reaction is complete, a solvent may be added to adjust the concentration to the desired level. As a synthesis means, in addition to solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization may be used.
[0038] 重量平均分子量が 3, 000〜50, 000であるアクリル系のアルカリ可溶性高分子に ついて説明する。重量平均分子量が 3, 000〜50, 000であるアクリル系のアルカリ 可溶性高分子の含有量は、 1〜40質量％である。支持層から基材への転写性、ラミ ネート性の観点から 1質量％以上であり、感度、密着性、線幅安定性の観点から 40 質量％以下である。含有量は、 5〜40質量％が好ましぐ 8〜20質量％がより好まし ぐ 8〜15質量％がさらに好ましい。また、その重量平均分子量は、顔料の分散安定 性の観点力 50, 000以下が好ましぐ適度なアルカリ現像性と密着性を維持する観 点から 3, 000以上である。重量平均分子量は、より好ましくは 5, 000以上 30, 000 以下、更に好ましくは、 10, 000以上 30, 000以下である。分子量は、上記と同様の 測定方法によって求めることができる。  [0038] An acrylic alkali-soluble polymer having a weight average molecular weight of 3,000 to 50,000 will be described. The content of the acrylic alkali-soluble polymer having a weight average molecular weight of 3,000 to 50,000 is 1 to 40% by mass. It is 1% by mass or more from the viewpoint of transferability from the support layer to the substrate and lamination, and 40% by mass or less from the viewpoints of sensitivity, adhesion, and line width stability. The content is preferably 5 to 40% by mass, more preferably 8 to 20% by mass, and still more preferably 8 to 15% by mass. In addition, the weight average molecular weight is 3,000 or more from the viewpoint of maintaining moderate alkali developability and adhesion, which are preferred from the viewpoint of dispersion stability of pigments of 50,000 or less. The weight average molecular weight is more preferably 5,000 or more and 30,000 or less, and still more preferably 10,000 or more and 30,000 or less. The molecular weight can be determined by the same measurement method as described above.
[0039] 重量平均分子量が 3, 000〜50, 000であるアクリル系のアルカリ可溶性高分子は 、カルボキシル基の量が酸当量で 200〜2, 000であること力好ましい。酸当量とは、 1当量のカルボキシル基を有する線状重合体の質量を示す。現像性の観点から酸当 量は 2, 000以下が好ましぐ現像後に黒色顔料が基板へ付着するのを抑制する観 点から、酸当量は 200以上が好ましい。その酸当量は 300〜900がより好ましぐ 40 0〜800がさらに好ましい。酸当量は、上記と同様の測定方法によって求めることが できる。 [0040] 重量平均分子量が 3, 000〜50, 000であるアクリル系のアルカリ可溶性高分子は 、アルキル (メタ）アタリレート、例えば、メチル (メタ)アタリレート、ェチル (メタ)アタリレ ート、 n—ブチル（メタ）アタリレート、 iso—ブチル（メタ）アタリレート、 sec—ブチル（メタ )アタリレート、 tert—ブチル (メタ）アタリレート、 2—ェチルへキシル (メタ）アタリレート 側鎖にヒドロキシル基を有する (メタ)アタリレート、例えば、 2—ヒドロキシェチル (メタ） アタリレート、 2—ヒドロキシプロピル (メタ）アタリレート、グリセロールモノ（メタ）アタリレ ート、 [0039] An acrylic alkali-soluble polymer having a weight average molecular weight of 3,000 to 50,000 preferably has a carboxyl group content of 200 to 2,000 in terms of acid equivalent. The acid equivalent refers to the mass of a linear polymer having 1 equivalent of a carboxyl group. The acid equivalent is preferably 2,000 or less from the viewpoint of developability. From the viewpoint of suppressing the black pigment from adhering to the substrate after development, the acid equivalent is preferably 200 or more. The acid equivalent is preferably 300 to 900, more preferably 400 to 800. The acid equivalent can be determined by the same measurement method as described above. [0040] An acrylic alkali-soluble polymer having a weight average molecular weight of 3,000 to 50,000 is an alkyl (meth) acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n -Butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate A hydroxyl group in the side chain (Meth) acrylate, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate,
脂環式側鎖を有する (メタ)アタリレート、例えば、シクロへキシル (メタ)アタリレート、ィ ソボル-ル (メタ）アタリレート、ジシクロペンタ-ル (メタ）アタリレート、ジシクロペンタジ ェ-ル (メタ）アタリレート、ァダマンチル (メタ）アタリレート、 その他、例えば、（メタ)アクリルアミド、 （メタ)アクリロニトリル、フエ-ル (メタ）アタリレ ート、グリシジル (メタ）アタリレート、スチレン力 選ばれる一種以上の化合物と、カル ボン酸を有する化合物、例えば (メタ)アクリル酸とを共重合したアルカリ可溶性高分 子を挙げることが出来る。ブラックマトリックスとして用いた場合の断面形状の観点から 、スチレンとメタクリル酸メチルとメタクリル酸を共重合した分子量 10, 000〜30, 000 の高分子が好ましい。  (Meth) acrylate having alicyclic side chain, for example, cyclohexyl (meth) acrylate, isobolol (meth) acrylate, dicyclopental (meth) acrylate, dicyclopentadiol (meth) Atalylate, adamantyl (meth) atarylate, and others, for example, (meth) acrylamide, (meth) acrylonitrile, phenol (meth) acrylate, glycidyl (meth) acrylate, styrene power and one or more compounds selected Examples thereof include compounds having a carboxylic acid, such as alkali-soluble polymers copolymerized with (meth) acrylic acid. From the viewpoint of the cross-sectional shape when used as a black matrix, a polymer having a molecular weight of 10,000 to 30,000 obtained by copolymerizing styrene, methyl methacrylate and methacrylic acid is preferable.
[0041] 上記式 (I)で表されるアルカリ可溶性高分子：上述した重量平均分子量が 3, 000 〜100, 000であるメタクリル酸べンジル又はアクリル酸ベンジルを共重合したアル力 リ可溶性高分子及び重量平均分子量が 3, 000〜50, 000であるアクリル系のアル カリ可溶性高分子力 なる群より選ばれる少なくとも一種のアルカリ可溶性高分子 (質 量比） = 1： 5〜16： 1である。その質量比は、感度、密着性、線幅再現性の観点から 1 : 5以上であり、支持層への塗工性、転写性の観点から 16 : 1以下である。  [0041] Alkali-soluble polymer represented by the above formula (I): Al-force-resoluble polymer obtained by copolymerization of benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 as described above. And at least one alkali-soluble polymer (weight ratio) selected from the group consisting of acrylic alcohol-soluble polymer having a weight average molecular weight of 3,000 to 50,000 is 1: 5 to 16: 1 . The mass ratio is 1: 5 or more from the viewpoint of sensitivity, adhesion, and line width reproducibility, and 16: 1 or less from the viewpoint of coating property to the support layer and transferability.
[0042] その質量比が 1： 5〜5： 1であることが好ま 、。感度、密着性、線幅再現性の観点 から、 1 : 5以上が好ましい。支持層への塗工性、転写性の観点から 5 : 1以下がより好 ましい。 1 : 3〜3 : 1が更に好ましい。  [0042] The mass ratio is preferably 1: 5 to 5: 1. In view of sensitivity, adhesion, and line width reproducibility, 1: 5 or more is preferable. From the viewpoint of coating property to the support layer and transferability, 5: 1 or less is more preferable. It is more preferable that the ratio is 1: 3 to 3: 1.
[0043] 上記式 (I)で表されるアルカリ可溶性高分子：上述した重量平均分子量が 3, 000 〜100, 000であるメタクリル酸べンジル又はアクリル酸ベンジルを共重合したアル力 リ可溶性高分子 (質量比） = 1： 5〜16： 1である。その質量比は、感度、密着性、線幅 再現性の観点から 1:5以上であり、支持層への塗工性、転写性の観点から 16:1以 下である。 [0043] Alkali-soluble polymer represented by the above formula (I): Al force obtained by copolymerization of benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 as described above. Re-soluble polymer (mass ratio) = 1: 5 to 16: 1. The mass ratio is 1: 5 or more from the viewpoint of sensitivity, adhesion, and line width reproducibility, and is 16: 1 or less from the viewpoint of coating property to the support layer and transferability.
[0044] その質量比が 1： 5〜5： 1であることが好ま 、。感度、密着性、線幅再現性の観点 から、 1:5以上が好ましい。支持層への塗工性、転写性の観点から 5:1以下がより好 ましい。 1:3〜3:1が更に好ましい。  [0044] The mass ratio is preferably 1: 5 to 5: 1. In view of sensitivity, adhesion, and line width reproducibility, 1: 5 or more is preferable. A ratio of 5: 1 or less is more preferable from the viewpoint of coating property to the support layer and transferability. A ratio of 1: 3 to 3: 1 is more preferable.
[0045] 上記式 (I)で表されるアルカリ可溶性高分子：重量平均分子量が 3, 000〜50, 00 0であるアクリル系のアルカリ可溶性高分子（質量比） =1:5〜16:1である。その質 量比は、 1:3〜5:1であることが好ましい。感度、密着性、線幅安定性の観点から、 1 :3以上が好ましい。支持層への塗工性、転写性の観点から 5:1以下が好ましい。 1: 1〜3:1がより好ましい。  [0045] The alkali-soluble polymer represented by the above formula (I): an acrylic alkali-soluble polymer (mass ratio) having a weight average molecular weight of 3,000 to 50,000, 000 = 1: 5 to 16: 1 It is. The mass ratio is preferably 1: 3 to 5: 1. From the viewpoint of sensitivity, adhesion, and line width stability, 1: 3 or more is preferable. From the viewpoint of coatability to the support layer and transferability, 5: 1 or less is preferable. 1: 1 to 3: 1 is more preferable.
[0046] 感光性榭脂組成物中には、該重量平均分子量が 3, 000〜100, 000であるメタク リル酸べンジル又はアクリル酸ベンジルを共重合したアルカリ可溶性高分子及び重 量平均分子量が 3, 000-50, 000であるアクリル系のアルカリ可溶性高分子からな る群より選ばれる少なくとも一種のアルカリ可溶性高分子以外にも、耐熱性、ブラック マトリックスの断面形状、耐薬品性、着色顔料の分散性などを考慮して、その他アル カリ可溶性高分子を併用することが出来る。その他アルカリ可溶性高分子としては、 カルボキシメチルセルロース、カルボキシェチルセルロース、力ノレボキシプロピノレセ ノレロース、ヒドロキシメチノレセノレロース、ヒドロキシェチノレセノレロース、ヒドロキシプロピ ルセルロースのヒドロキシル基に多塩基酸無水物を反応させたセルロース榭脂、ノボ ラック榭脂、などを挙げることが出来る。  [0046] The photosensitive resin composition has an alkali-soluble polymer copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 and a weight average molecular weight. In addition to at least one alkali-soluble polymer selected from the group consisting of acrylic alkali-soluble polymers of 3,000-50,000, heat resistance, black matrix cross-sectional shape, chemical resistance, color pigment In consideration of dispersibility, other alkali-soluble polymers can be used in combination. Other alkali-soluble polymers include carboxymethylcellulose, carboxyethylcellulose, force norepropoxypropenorenosellose, hydroxymethinorecenorelose, hydroxyethinoresenorelose, and hydroxypropylcellulose with a polybasic acid anhydride. Examples thereof include cellulose resin and novolac resin obtained by reacting products.
[0047] 本発明の感光性榭脂積層体は、感光性榭脂組成物中に、エチレン性不飽和二重 結合を有する光重合性ィ匕合物を 3〜25質量％含む。現像性の観点から 3質量％以 上であり、密着性の観点から 25質量％以下である。 25質量％以下とすることで、適 切な現像時間を確保し、十分に安定した密着性を確保することが出来る。その含有 量は 5〜20質量％がより好ましぐ 5〜15質量％がさらに好ましい。  [0047] The photosensitive resin laminate of the present invention contains 3 to 25% by mass of a photopolymerizable compound having an ethylenically unsaturated double bond in the photosensitive resin composition. From the viewpoint of developability, it is 3% by mass or more, and from the viewpoint of adhesion, it is 25% by mass or less. By setting it to 25% by mass or less, an appropriate development time can be secured, and sufficiently stable adhesion can be secured. The content is more preferably 5 to 20% by mass, and further preferably 5 to 15% by mass.
[0048] エチレン性不飽和二重結合を有する光重合性ィ匕合物としては、下記式 (ΠΙ)で表さ れる化合物を含むことが好ま U、。その含有量は密着性の観点から感光性榭脂組成 物中の固形分全体基準とした場合の 2質量％以上が好ましぐ転写性の観点力 20 質量％以下が好ましい。 [0048] The photopolymerizable compound having an ethylenically unsaturated double bond preferably includes a compound represented by the following formula (I). Its content is photosensitive resin composition from the viewpoint of adhesion From the viewpoint of transferability, 2% by mass or more based on the total solid content in the product is preferable. 20% by mass or less is preferable.
[0049] [化 6] [0049] [Chemical 6]
Figure imgf000015_0001
Figure imgf000015_0001
[0050] (式 (ΠΙ)中、 R 、 Rおよび Rは、それぞれ互いに独立な Hまたは CH基を表す。 R [0050] (In the formula (R), R 1, R and R each independently represent an H or CH group. R
3 4 5 3 6 は 2価の連結基で、炭素数 2〜8のアルキレン基、炭素数 3〜 10のシクロアルキレン 基、及び炭素数 6〜10のフエ-レン基力もなる群より選ばれる一種の基を表す。 ) 上記式 (ΠΙ)で示される化合物としては、コハク酸変性ペンタエリスリトールトリ（メタ） アタリレート、フタル酸変性ペンタエリスリトールトリ（メタ）アタリレート、イソフタル酸変 性ペンタエリスリトールトリ（メタ）アタリレート、テレフタル酸変性ペンタエリスリトールトリ (メタ)アタリレート、などが挙げられる。密着性の観点から、コハク酸変性ペンタエリス リトールトリアタリレートが好ましい。  3 4 5 3 6 is a divalent linking group selected from the group consisting of an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, and a phenyl group having 6 to 10 carbon atoms. Represents a group of ) Succinic acid-modified pentaerythritol tri (meth) acrylate, phthalic acid modified pentaerythritol tri (meth) acrylate, isophthalic acid modified pentaerythritol tri (meth) acrylate, And terephthalic acid-modified pentaerythritol tri (meth) acrylate. From the viewpoint of adhesion, succinic acid-modified pentaerythritol tritalylate is preferable.
[0051] 上記式 (ΠΙ)で示される化合物以外のエチレン性不飽和二重結合を有する光重合 性化合物としては、たとえば、ビスフエノール Aの両端にそれぞれ平均 2モルのプロピ レンオキサイドと平均 6モルのエチレンオキサイドを付カ卩したポリアルキレングリコール のジメタタリレートや、ビスフエノール Aの両端にそれぞれ平均 5モルのエチレンォキ サイドを付加したポリエチレングリコ—ルのジメタタリレート (新中村化学工業 (株)製 N Kエステル BPE— 500)、 1, 6—へキサンジオールジ (メタ）アタリレート、 1, 4—シク 口へキサンジォ—ルジ (メタ）アタリレート、ポリプロピレングリコ—ルジ (メタ）アタリレー ト、ポリエチレングリコールジ (メタ）アタリレート、 2—ジ（p—ヒドロキシフエ-ル）プロパ ンジ (メタ）アタリレート、グリセ口—ルトリ（メタ）アタリレート、トリメチ口—ルプロパントリ（ メタ）アタリレート、ポリオキシプロピルトリメチ口一ルプロパントリ（メタ）アタリレート、ポリ ォキシェチルトリメチロ—ルプロパントリアタリレート、ペンタエリスリトールテトラ（メタ） アタリレート、ジペンタエリスリトールペンタ（メタ）アタリレート、トリメチロールプロパント リグリシジルェ—テルトリ（メタ）アタリレート、ビスフエノ―ル Aジグリシジルェ—テルジ（ メタ）アタリレート及び、 13—ヒドロキシプロピル一 13， - (アタリロイルォキシ）プロピル フタレート、フエノキシポリエチレングリコ一ル (メタ）アタリレート、ノユルフェノキシポリ エチレングリコール (メタ）アタリレート、ノユルフェノキシポリアルキレングリコール (メタ )アタリレート、ポリプロピレングリコールモノ (メタ）アタリレートが挙げられる。密着性の 観点から、ペンタエリスリトールテトラ (メタ)アタリレートが好ましぐ上記式 (III)の化合 物と組み合わせて用いることがさらに好まし!/、。 [0051] Examples of the photopolymerizable compound having an ethylenically unsaturated double bond other than the compound represented by the above formula (ΠΙ) include, for example, an average of 2 mol of propylene oxide and an average of 6 mol at both ends of bisphenol A, respectively. Polyalkylene glycol dimetatalylate with the addition of ethylene oxide and polyethylene glycol dimetatalylate with an average of 5 moles of ethylene oxide on each end of bisphenol A (manufactured by Shin-Nakamura Chemical Co., Ltd.) NK ester BPE—500), 1, 6-hexanediol di (meth) acrylate, 1, 4—sucral hexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, 2-di (p-hydroxyphenol) propylene (meth) acrylate, Glyce - Rutori (meth) Atari rate, trimethylene port - Rupuropantori (meth) Atari rate, polyoxypropylated trimethylolpropane opening one Rupuropantori (meth) Atari, poly Oxetiltrimethylolpropane tritalylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylol propantriglicidyl tertri (meth) acrylate, bisphenol A diglycidyl -Terdi (meth) acrylate and 13-hydroxypropyl-13,-(talylyloxy) propyl phthalate, phenoxypolyethylene glycol (meth) acrylate, nourphenoxypolyethylene glycol (meth) acrylate , Nourphenoxy polyalkylene glycol (meth) acrylate, and polypropylene glycol mono (meth) acrylate. From the viewpoint of adhesion, it is further preferred to use in combination with the compound of the above formula (III), where pentaerythritol tetra (meth) acrylate is preferred!
[0052] さらに、例えば、 2 ヒドロキシェチル (メタ）アタリレートにエチレンオキサイドを 1〜3 モル付カ卩した化合物とへキサヒドロフタル酸とのハーフエステル化合物、 2—ヒドロキ シェチル (メタ）アタリレートにエチレンオキサイドを 1〜3モル付カ卩した化合物とコハク 酸とのハーフエステル化合物、 2—ヒドロキシェチル（メタ）アタリレートにエチレンォキ サイドを 1〜3モル付カ卩した化合物とイソフタル酸とのハーフエステル化合物、 2 ヒド ロキシェチル (メタ）アタリレートにエチレンオキサイドを 1〜3モル付カ卩した化合物とテ レフタル酸とのハーフエステル化合物が挙げられる。  [0052] Further, for example, a half ester compound of 2-hydroxyethyl (meth) acrylate with 1 to 3 moles of ethylene oxide and hexahydrophthalic acid, 2-hydroxy shetyl (meth) acrylate A half-ester compound of succinic acid with a compound with 1 to 3 moles of ethylene oxide added thereto, and a compound with 1 to 3 moles of ethylene oxide with 2-hydroxyethyl (meth) acrylate and isophthalic acid. A half ester compound, a compound obtained by adding 1 to 3 moles of ethylene oxide to 2-hydroxychetyl (meth) acrylate and a half ester compound of terephthalic acid.
[0053] さらに、例えば、ジイソシァネートイ匕合物、例えば、へキサメチレンジイソシァネート、 トリレンジイソシァネート、又は 2, 2, 4 トリメチルへキサメチレンジイソシァネートと、 一分子中にヒドロキシル基と (メタ)アクリル基を有する化合物、例えば、 2—ヒドロキシ プロピルアタリレート、オリゴプロピレングリコールモノメタタリレート、とを反応させて得 られるウレタン化合物等が挙げられる。具体的には、へキサメチレンジイソシァネート とオリゴプロピレングリコールモノメタタリレート（日本油脂 (株)製、ブレンマー PP100 [0053] Further, for example, a diisocyanate compound such as hexamethylene diisocyanate, tolylene diisocyanate, or 2,2,4 trimethylhexamethylene diisocyanate, and one molecule Examples thereof include a urethane compound obtained by reacting a compound having a hydroxyl group and a (meth) acrylic group, for example, 2-hydroxypropyl acrylate, oligopropylene glycol monomethacrylate. Specifically, hexamethylene diisocyanate and oligopropylene glycol monometatalylate (Nippon Yushi Co., Ltd., Bremer PP100
0)とを反応させて得られる化合部を挙げることが出来る。 The compound part obtained by making 0) react can be mentioned.
[0054] 本発明の感光性榭脂積層体は、感光性榭脂組成物中に、光重合開始剤を 0. 1〜 20質量％含む。感度、密着性の観点から 0. 1質量％以上であり、線幅再現性の観 点から 20質量％以下である。その含有量は 1〜10質量％がより好ましぐ 1〜5質量 %がさらに好ましい。 [0054] The photosensitive resin laminate of the present invention contains 0.1 to 20% by mass of a photopolymerization initiator in the photosensitive resin composition. From the viewpoint of sensitivity and adhesion, it is 0.1% by mass or more, and from the viewpoint of line width reproducibility, it is 20% by mass or less. The content is more preferably 1 to 5% by mass, more preferably 1 to 10% by mass.
[0055] 光重合開始剤としては、ォキシムエステルイ匕合物であることが好ま 、。具体的に は、ォキシムエステル類、例えば、 1—フエ-ル— 1, 2—プロパンジオン— 2— O ベ ンゾィルォキシム、及び 1 フエ-ルー 1, 2—プロパンジオン— 2—（O エトキシカ ルポ-ル)ォキシムや、特表 2004— 534797号公報に記載の化合物を上げることが 出来る。なかでも、下記式 (IV)で表される化合物が好ましい。 [0055] The photopolymerization initiator is preferably an oxime ester compound. Specifically Are oxime esters such as 1-phenol-1,2-propanedione-2-O-benzoyloxime, and 1-fluoro-1,2-propanedione-2- (O ethoxycarbon) oxime. In addition, the compounds described in JP-T-2004-534797 can be raised. Among these, a compound represented by the following formula (IV) is preferable.
[0056] [化 7] [0056] [Chemical 7]
Figure imgf000017_0001
Figure imgf000017_0001
[0057] 上記式 (IV)で表される化合物の具体例は、 1 [9ーェチルー 6—（2 メチルベン ゾィル） 9. H. —力ルバゾール—3—ィル]—ェタン— 1—オンォキシム— O ァセ テート（チノく.スぺシャリティ.ケミカルズ製 IRGACURE OXE— 02)である。 [0057] Specific examples of the compound represented by the above formula (IV) are as follows: 1 [9-ethyl-6- (2 methylbenzol) 9. H. —force rubazol-3-yl] -ethane-1-onoxime-O Acetate (IRGACURE OXE-02 from Chinoku. Specialty Chemicals).
[0058] 本発明の感光性榭脂積層体は、感光性榭脂組成物中に、上記式 (IV)以外の光重 合開始剤、増感剤、連鎖移動剤などを組み合わせて用いても良い。  [0058] The photosensitive resin laminate of the present invention may be used in combination with a photopolymerization initiator, a sensitizer, a chain transfer agent, and the like other than the above formula (IV) in the photosensitive resin composition. good.
[0059] 上記式 (IV)以外の光重合開始剤としては、例えば、以下のものが挙げられる。チ ォキサントン、 2, 4 ジェチルチオキサントン、イソプロピルチォキサントン、 2 クロ口 チォキサントン、 2, 4, 5 トリアリーノレイミダゾーノレ二量体類、例えば、 2- (o クロ口 フエ-ル）— 4, 5 ジフエ-ルイミダゾ—ルニ量体、 2— (o クロ口フエ-ル）— 4, 5 —ビス一（m—メトキシフエ-ル）イミダゾ一ルニ量体、 2— (p—メトシキフエ-ル） 4 , 5—ジフエ-ルイミダゾ—ルニ量体。また、 p ァミノフエ-ルケトン類、例えば、 p— ァミノべンゾフエノン、 p ブチルァミノフエノン、 p ジメチルアミノアセトフエノン、 p— ジメチルァミノべンゾフエノン、 p, p，一ビス（ェチルァミノ）ベンゾフエノン、 p, p，一ビス (ジメチルァミノ）ベンゾフエノン [ミヒラーズケトン]、 p, p，一ビス（ジェチルァミノ）ベン ゾフエノン、 p, p '—ビス（ジブチルァミノ）ベンゾフエノンが挙げられる。また、キノン類 、例えば、 2—ェチルアントラキノン、 2— tert—ブチルアントラキノン、芳香族ケトン類 、例えば、ベンゾフエノン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインェチル エーテル等のベンゾインエーテル類。アタリジン化合物、例えば、 9 フエ-ルアタリ ジン。トリアジン系ィ匕合物、例えば、 2, 4, 6 トリクロ s—トリアジン、 2 フエ- —4, 6 ビス（トリクロロメチル） s トリァジン、 2— (p—メトキシフエ-ル 4, 6— ビス（トリクロロメチル） s トリァジン、 2— (p トリル） 4, 6 ビス（トリクロロメチル） —s トリァジン、 2 ピぺ口-ル一 4, 6 ビス（トリクロロメチル） s トリァジン、 2, 4 —ビス（トリクロロメチル） 6—スチリル一 s トリァジン、 2— (ナフト一 1—ィル） 4, 6 ビス（トリクロロメチル） s トリァジン、 2— (4—メトキシ一ナフト一 1—ィル） 4, 6 ビス（トリクロロメチル） s トリァジン、 2, 4 トリクロロメチル一（ピぺ口-ル） 6 —トリァジン、 2, 4 トリクロロメチル（4'—メトキシスチリル） 6 トリアジン。その他、 ベンジルジメチルケタール、ベンジルジェチルケタール、 2—べンジルージメチルアミ ノー 1— (4 モルフォリノフエ-ル）一ブタノン一 1、ビス（2, 4, 6 トリメチルベンゾィ ル） フエ-ルホスフィンオキサイド、 2—メチルー 2 モルフオリノー 1 4 （メチル チォフエ-ル） プロパン 1 オン等公知の種々の化合物が挙げられる。 [0059] Examples of the photopolymerization initiator other than the above formula (IV) include the following. Thioxanthone, 2, 4 Jetylthioxanthone, Isopropyl thixanthone, 2 Chloxone Thioxanthone, 2, 4, 5 Triarynoreidazonole dimers, for example, 2- (o black mouth phenol) — 4, 5 Diphenol-Lumimidazolnimer, 2— (o Black Mole), 4, 5 — Bis (m-methoxyphenol) imidazole Lunimer, 2— (p-methoxyphenol) 4, 5 —Gihue-Louimidazolnimer. In addition, p-aminophenol ketones such as p-aminominobenzophenone, p-butylaminophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p, monobis (ethylamino) benzophenone, p, p, Bis (dimethylamino) benzophenone [Michler's ketone], p, p, bis (jetylamino) ben Zofenone, p, p'-bis (dibutylamino) benzophenone. Moreover, quinones, for example, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, aromatic ketones, for example, benzoin ethers such as benzophenone, benzoin, benzoin methyl ether, and benzoin ethyl ether. Atalidine compounds, such as 9-phenol atalidine. Triazine compounds, such as 2, 4, 6 trichloro s-triazine, 2 phe- —4, 6 bis (trichloromethyl) s triazine, 2— (p-methoxyphenol 4, 6-bis (trichloromethyl) ) S triazine, 2— (p-tolyl) 4, 6 bis (trichloromethyl) — s triazine, 2 pipetyl 4, 6 bis (trichloromethyl) s triazine, 2, 4 — bis (trichloromethyl) 6 —Styryl 1 s triazine, 2— (Naphtho 1-yl) 4,6 bis (trichloromethyl) s Triazine, 2— (4-methoxy 1 naphth 1-yl) 4,6 bis (trichloromethyl) s Triazine, 2, 4 Trichloromethyl mono (pipetyl) 6-Triazine, 2, 4 Trichloromethyl (4'-methoxystyryl) 6 Triazine, Others Benzyldimethyl ketal, Benzyl jetyl ketal, 2-Benzyl -Dimethylamino 1- (4 morpholinophenol) 1-butanone 1, bis (2, 4, 6 trimethylbenzoyl) phenol phosphine oxide, 2-methyl-2 morpholino 1 4 (methyl thiophenol) Propane 1 Various known compounds such as ON can be mentioned.
また、増感剤としては、例えば、 N ァリールグリシン、メルカプトトリァゾール誘導体 、メルカプトテトラゾール誘導体、メルカプトチアジアゾール誘導体、また、連鎖移動 剤としては、例えば、へキサンジチオール、デカンジチオール、 1, 4 ブタンジォー ルビスチォプロピオネート、 1, 4 ブタンジオールビスチォグリコレート、エチレングリ コールビスチォグリコレート、エチレングリコーノレビスチォプロピオネート、トリメチロー ルプロパントリスチォグリコレート、トリメチロールプロパントリスチォプロピオネート、トリ メチロールプロパントリス（3—メルカプトブチレート）、ペンタエリスリトールテトラキスチ オダリコレート、ペンタエリスリトールテトラキスチォプロピオネート、トリメルカプトプロピ オン酸トリス（2 ヒドロキシェチル)イソシァヌレート、 1, 4 ジメチルメルカプトべンゼ ン、 2, 4, 6 トリメルカプト—s トリアジン、 2—(N, N—ジブチルァミノ）—4, 6 ジ メルカプト s トリァジン等の多官能チオールなど公知の種々の化合物が挙げられ る。 [0061] 本発明の感光性榭脂積層体は、感光性榭脂組成物中に、着色顔料を 40〜70質 量％含む。遮光性の観点力 40質量％以上であり、転写性、ブラックマトリックスの密 着性、線幅安定性、形状の観点から 70質量％以下である。その含有量は 45〜65質 量％が好ましく、 50〜65質量％がさらに好まし 、。 Examples of sensitizers include N-aryglycine, mercaptotriazole derivatives, mercaptotetrazole derivatives, mercaptothiadiazole derivatives, and chain transfer agents such as hexanedithiol, decandithiol, and 1,4 butanediolbis. Thiopropionate, 1, 4 Butanediol bisthioglycolate, Ethylene glycol bisthioglycolate, Ethylene glycol norebisthiopropionate, Trimethylolpropane tristiglycolate, Trimethylolpropane tristipropionate, Tri Methylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisti odalicolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionate tris 2 hydroxyethyl) isocyanurate, 1,4 dimethylmercaptobenzene, 2,4,6 trimercapto-s triazine, 2— (N, N-dibutylamino) —4,6 dimercapto s triazine, etc. Various known compounds can be mentioned. [0061] The photosensitive resin laminate of the present invention contains 40 to 70 mass% of a coloring pigment in the photosensitive resin composition. The light-shielding viewpoint power is 40% by mass or more, and it is 70% by mass or less from the viewpoints of transferability, black matrix adhesion, line width stability, and shape. Its content is preferably 45 to 65% by mass, more preferably 50 to 65% by mass.
[0062] 上記着色顔料としては、ァゾ系、フタロシアニン系、インジゴ系、アントラキノン系、 ペリレン系、キナクリドン系、メチン'ァゾメチン系、イソインドリノン系などの有機顔料 や、カーボンブラック類、チタンブラック、チタン酸窒化物、黒色低次酸化チタン、ダラ ファイト粉末、鉄黒、酸化銅などの無機顔料があり、複数の顔料を含んでも構わない 。これらの顔料には、感光性榭脂組成物での分散性を高めるため、あるいは電気抵 抗値を高めるための表面処理がなされて 、てもよ 、。  [0062] Examples of the coloring pigment include organic pigments such as azo, phthalocyanine, indigo, anthraquinone, perylene, quinacridone, methine'azomethine, and isoindolinone, carbon blacks, titanium black, There are inorganic pigments such as titanium oxynitride, black low-order titanium oxide, dulphite powder, iron black, and copper oxide, and a plurality of pigments may be included. These pigments may be subjected to a surface treatment to increase the dispersibility in the photosensitive resin composition or to increase the electric resistance value.
[0063] 有機顔料としては、例えば、カラーインデックス（C. I. ； The Society of Dyers an d Colourists社発行）において、ビグメント（Pigment)に分類されている化合物、具 体的には、下記のようなカラーインデックス (C. I. )番号が付されているものを挙げる ことが出来る。以下に、列記する。  [0063] Examples of organic pigments include compounds classified as Pigments in the Color Index (CI; published by The Society of Dyers and Colors), and specifically the following Color Index Listed with (CI) number. Listed below.
[0064] C. I.ビグメン卜レッド 9、 C. I.ビグメン卜レッド 97、 C. I.ビグメン卜レッド 105、 C. I. ビグメン卜レッド 122、 C. I.ビグメン卜レッド 123、 C. I.ビグメン卜レッド 144、 C. I.ピ グメントレッド 149、 C. I.ビグメントレッド 166、 C. I.ビグメントレッド 168、 C. I.ピグメ ン卜レッド 176、 C. I. ビグメン卜レッド 177、 C. I.ビグメン卜レッド 180、 C. I.ビグメン トレッド 192、 C. I.ビグメントレッド 215、 C. I.ビグメントレッド 216、 C. I.ビグメントレ ッド 224、 C. I.ビグメントレッド 242、 C. I.ビグメントレッド 254、 C. I.ビグメンレッド 264、 C. I.ビグメン卜レッド 265。  [0064] CI Pigment Red 9, CI Big Red 97, CI Big Red 105, CI Big Red 122, CI Big Red 123, CI Big Red 144, CI Pigment Red 149, CI Big Red 166 CI Pigment Red 168, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Tread 192, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Red 265.
[0065] 更に、 C. I.ビグメントオレンジ 13、 C. I.ビグメントオレンジ 31、 C. I.ビグメントォレ ンジ 36、 C. I.ビグメントオレンジ 38、 C. I.ビグメントオレンジ 40、 C. I.ピグメントォ レンジ 42、 C. I.ビグメントオレンジ 43、 C. I.ビグメントオレンジ 51、 C. I.ビグメント オレンジ 55、 C. I.ビグメントオレンジ 59、 C. I.ビグメントオレンジ 61、 C. I.ビグメン トオレンジ 64、 C. I.ビグメントオレンジ 65、 C. I.ビグメントオレンジ 71、 C. I.ピグメ ントオレンジ 73。  [0065] Furthermore, CI Pigment Orange 13, CI Pigment Orange 31, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigmento Range 42, CI Pigment Orange 43, CI Pigment Orange 51 CI pigment orange 55, CI pigment orange 59, CI pigment orange 61, CI pigment orange 64, CI pigment orange 65, CI pigment orange 71, CI pigment orange 73.
[0066] 更に、 C. I.ビグメントイエロー 1、 C. I.ビグメントイエロー 3、 C. I.ビグメントイエロ 一 12、 C. I.ビグメントイエロー 13、 C. I.ビグメントイエロー 14、 C. I.ビグメントイエ ロー 15、 C. I.ビグメントイエロー 16、 C. I.ビグメントイエロー 17、 C. I.ビグメントイ エロー 20、 C. I.ピグメントイエロー 24、 C. I.ピグメントイエロー 31、 C. I.ピグメント イェロー 53、 C. I.ビグメントイエロー 83、 C. I.ビグメントイエロー 86、 C. I.ビグメン トイエロー 93、 C. I.ビグメントイエロー 94、 C. I.ビグメントイエロー 109、 C. I.ピグメ ン卜イェロー 110、 C. I.ビグメン卜イェロー 117、 C. I.ビグメン卜イェロー 125、 C. I. ビグメントイエロー 128、 C. I.ビグメントイエロー 137、 C. I.ビグメントイエロー 138、 C. I.ビグメントイエロー 139、 C. I.ビグメントイエロー 147、 C. I.ビグメントイエロー 148、 C. I.ビグメン卜イェロー 150、 C. I.ビグメン卜イェロー 153、 C. I.ピグメン卜ィ エロー 154、 C. I.ビグメントイエロー 166、 C. I.ビグメントイエロー 173。 [0066] In addition, CI pigment yellow 1, CI pigment yellow 3, CI pigment yellow 1 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 53, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 117, CI Pigment Yellow Yellow 125 , CI Pigment Yellow 128, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigmention Yellow 154, CI Pigment Yellow 166 CI Pigment Yellow 173.
[0067] 更に、 C. I.ビグメントグリーン 7、 C. I.ビグメントグリーン 36、 C. I.ビグメントブル 一 15、 C. I.ビグメントブルー 15 : 3、 C. I.ビグメントブルー 15 :4、 C. I.ピグメントブ ルー 15 : 6、 C. I.ビグメントブルー 60、 C. I.ピグメントノィォレット 1、 C. I.ビグメント ノ ィォレゝノト 19、 C. I.ピグメントノィォレ、ノト 23、 C. I.ピグメントノィォレ、ノト 29、 C. I .ビグメントバイオレット 32、 C. I.ビグメントバイオレット 36、 C. I.ビグメントバイオレツ ト 38、 C. I.ビグメントブラウン 23、 C. I.ビグメントブラウン 25、 C. I.ビグメントブラッ ク 1、 C. I.ビグメントブラック 7。  [0067] In addition, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Bull 1 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60 CI Pigment Nooret 1, CI Pigment Nore 19, CI Pigment Nore, Noto 23, CI Pigment Nore, Noto 29, C.I. Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black 7.
[0068] 染料としては、例えば、フクシン、フタロシアニングリーン、オーラミン塩基、カルコキ シドグリーン S,パラマジェンタ、クリスタルバイオレット、メチルオレンジ、ナイルブル 一 2B、ビクトリアブルー、マラカイトグリーン (保土ケ谷ィ匕学 (株)製アイゼン (登録商 標） MALACHITE GREEN)、べィシックブルー 20、ダイアモンドグリーン（保土ケ 谷化学 (株)製アイゼン（登録商標） DIAMOND GREEN GH)等が挙げられる。  [0068] Examples of the dye include fuchsin, phthalocyanine green, auramin base, calcidoside green S, paramagenta, crystal violet, methyl orange, Nile Blue 1B, Victoria blue, malachite green (Eisen, Hodogaya Chemical Co., Ltd.) (Registered trademark) MALACHITE GREEN), Basic Blue 20, Diamond Green (Hozengaya Chemical Co., Ltd. Aizen (registered trademark) DIAMOND GREEN GH) and the like.
[0069] 本発明の感光性榭脂積層体は、着色顔料が黒色顔料である場合ブラックマトリック ス形成材料として有用である。黒色顔料としては、上記に列挙した着色物質の内で 黒色であるものを挙げることが出来る。即ち、有機顔料としては、 C. I.ビグメントブラ ック 1、 C. I.ビグメントブラック 7など力 無機顔料としては、カーボンブラック類、チタ ンブラック、チタン酸窒化物、黒色低次酸化チタン、グラフアイト粉末、鉄黒、酸化銅、 などを挙げることが出来る。この他、 Cu、 Fe、 Mn、 Cr、 Co、 Ni、 V、 Zn、 Se、 Mg、 C a、 Sr、 Ba、 Pd、 Ag、 Cd、 In、 Sn、 Sb、 Hg、 Pb、 Bi、 Si及び Al等の各種金属酸ィ匕 物、複合酸化物、金属硫化物、金属硫酸鉛又は金属炭酸塩等の無機顔料も用いる ことができる。遮光性およびブラックマトリックスとしての感度、解像度、密着性への影 響の観点から、カーボンブラックが好ましい。ブラックマトリックスの絶縁性の観点から チタンブラックが好ましい。 [0069] The photosensitive resin laminate of the present invention is useful as a black matrix forming material when the color pigment is a black pigment. Examples of black pigments include those that are black among the colored substances listed above. In other words, organic pigments such as CI pigment black 1, CI pigment black 7, etc. Powerful inorganic pigments include carbon blacks, titanium black, titanium oxynitride, black low-order titanium oxide, graphite powder, iron black , Copper oxide, and the like. In addition, Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se, Mg, C Various metal oxides such as a, Sr, Ba, Pd, Ag, Cd, In, Sn, Sb, Hg, Pb, Bi, Si, and Al, composite oxides, metal sulfides, metal lead sulfate, or metal carbonate Inorganic pigments such as salts can also be used. Carbon black is preferred from the viewpoints of light shielding properties and sensitivity to black matrix, resolution, and adhesion. From the viewpoint of black matrix insulation, titanium black is preferred.
[0070] 好ましいカーボンブラックとしては、以下に例示するカーボンブラックの少なくとも 1 種を使用することができる。  [0070] As preferred carbon black, at least one carbon black exemplified below can be used.
[0071] 例えば、三菱ィ匕学社製のカーボンブラックとしては、カーボンブラック # 2400、 # 2 350、 #2300、 #2200、 #1000、 #980、 #970、 #960、 #950、 #900、 #85 0、 MCF88、 #650、 MA600、 MA7、 MA8、 MA11、 MA100、 MA220、 IL30 B、 IL31B、 IL7B、 IL11B、 IL52B、 #4000、 #4010、 #55、 #52、 #50、 #47 、 #45、 #44、 #40、 #33、 #32、 #30、 #20、 #10、 #5、CF9、 #3050、 #3 150、 #3250、 #3750、 # 3950、ダイヤブラック A、ダイヤブラック N220M、ダイ ャブラック N234、ダイヤブラック I、ダイヤブラック LI、ダイヤブラック II、ダイヤブラック N339、ダイヤブラック SH、ダイヤブラック SHA、ダイヤブラック LH、ダイヤブラック H 、ダイヤブラック HA、ダイヤブラック SF、ダイヤブラック N550M、ダイヤブラック E、ダ ィャブラック G、ダイヤブラック R、ダイヤブラック N760M、ダイヤブラック LPを挙げる ことが出来る。  [0071] For example, carbon black # 2400, # 2 350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 85 0, MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30 B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3 150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black N339, Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LP Can be mentioned.
[0072] キャンカーブ社製のカーボンブラックとしては、サーマックス N990、 N991、 N907 、 N908を挙げることができる。  [0072] Examples of carbon blacks manufactured by Cancarb may include THERMAX N990, N991, N907, and N908.
[0073] 旭カーボン社製のカーボンブラックとしては、旭 #80、旭 #70、旭 #70L、旭 F—2 00、旭 #66、旭 #66HN、旭 #60H、旭 #60U、旭 #60、旭 #55、旭 #50H、旭 #51、旭 # 50U、旭 # 50、旭 # 35、旭 # 15を挙げることが出来る。  [0073] Asahi Carbon's carbon blacks include Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-2200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60 , Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15.
[0074] デグサ社製のカーボンブラックとしては、 ColorBlack Fw200、 ColorBlack Fw2 、 ColorBlack Fw2V、 ColorBlackFwl、 ColorBlack Fwl8、 ColorBlack S170 、 ColorBlack S160、 SpecialBlack6、 SpecialBlack5、 SpecialBlack4、 Specia lBlack4A、 PrintexU、 PrintexV、 Printexl40U、 Printexl40Vを挙げることが 出来る。 [0075] キャボット社（Cabot Corporation)製のカーボンブラックとしては、リーガル (Regal；登 録商標）、ブラックパールズ（Black Pearls ;登録商標）、エルフテックス（Elftex ;登録商 標）、モナーク（Monarch ;登録商標）、モーダル (Mogul ;登録商標）、およびバルカン (Vulcan；登録商標）の商標名で販売されて!、るカーボンブラックを含む {例えばブラ ックパールズ (登録商標） 2000、ブラックパールズ (登録商標） 1400、ブラックパール ズ (登録商標） 1300、ブラックパールズ (登録商標） 1100、ブラックパールズ (登録商 標） 1000、ブラックパールズ (登録商標） 900、ブラックパールズ (登録商標） 880、ブ ラックパールズ (登録商標） 800、ブラックパールズ (登録商標） 700、ブラックパール ズ (登録商標) L、エルフテックス (登録商標） 8、モナーク (登録商標） 1400、モナーク (登録商標） 1300、モナーク (登録商標） 1100、モナーク (登録商標） 1000、モナ一 ク（登録商標） 900、モナーク (登録商標） 880、モナーク (登録商標） 800、モナーク（ 登録商標） 700、モーダル (登録商標) L、リーガル (登録商標） 330、リーガル (登録 商標) 400、バルカン (登録商標) P}を挙げることが出来る。 [0074] Degussa carbon black includes ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2V, ColorBlackFwl, ColorBlack Fwl8, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printexl40U, Printexl40V I can do it. [0075] Carbon blacks manufactured by Cabot Corporation include Regal (registered trademark), Black Pearls (registered trademark), Elftex (registered trademark), and Monarch (registered trademark). Trademark), Modal (Mogul), and Vulcan (trademark), including carbon black {eg Black Pearls (registered trademark) 2000, Black Pearls (registered trademark) 1400 , Black Pearls (registered trademark) 1300, Black Pearls (registered trademark) 1100, Black Pearls (registered trademark) 1000, Black Pearls (registered trademark) 900, Black Pearls (registered trademark) 880, Black Pearls (registered trademark) 800, Black Pearls (registered trademark) 700, Black Pearls (registered trademark) L, Elftex (registered trademark) 8, Monarch (registered) Trademark) 1400, Monarch (R) 1300, Monarch (R) 1100, Monarch (R) 1000, Monarch (R) 900, Monarch (R) 880, Monarch (R) 800, Monarch (R) (Registered Trademark) 700, Modal (Registered Trademark) L, Regal (Registered Trademark) 330, Regal (Registered Trademark) 400, and Vulcan (Registered Trademark) P}.
[0076] コロンビアケミカル社（Colombian Chemical Corporation)製カーボンブラックとして は、レイブン（Raven) 780、レイブン 890、レイブン 1020、レイブン 1040、レイブン 1255、レイブン 1500、レイブン 5000、レイブン 5250を挙げ、ること力 S出来る。  [0076] Carbon blacks from Colombian Chemical Corporation include Raven 780, Raven 890, Raven 1020, Raven 1040, Raven 1255, Raven 1500, Raven 5000, Raven 5250. I can do it.
[0077] 感光性榭脂組成物中には、分散剤等を含むことが出来る。後述の通り感光性榭脂 積層体は、感光性榭脂組成物を支持層に塗工することによって製造することが出来 るが、黒色顔料を予め分散剤等で溶剤に分散させてこれを加えて感光性榭脂組成 物とし、支持層に塗工して感光性榭脂層とすることもできる。  [0077] The photosensitive resin composition may contain a dispersant and the like. As will be described later, the photosensitive resin laminate can be produced by coating the photosensitive resin composition on the support layer, but the black pigment is previously dispersed in a solvent with a dispersant or the like and added. It can also be used as a photosensitive resin composition, which can be applied to the support layer to form a photosensitive resin layer.
[0078] 分散剤としては、例えば、ポリウレタン、ポリアタリレートなどのカルボン酸エステル、 不飽和ポリアミド、ポリカルボン酸（部分）アミン塩、ポリカルボン酸アンモ-ゥム塩、ポ リカルボン酸アルキルアミン塩、ポリシロキサン、水酸基含有ポリカルボン酸エステル や、これらの変性物、ポリ（低級アルキレンィミン）と遊離のカルボン酸基を有するポリ エステルとの反応により形成されたアミドやその塩があげられる。また、特開 2005— 2 5169号公報に記載の塩基性官能基を有する高分子分散剤を利用することが出来る 。また、具体的には、ビックケミ一社製の Disperbykl60、 Disperbykl61、 Disperb ykl62、 Disperbykl63、 Disperbvkl64、 Disperbykl66、ゼネカ社製の SOLSP ERSE20000、 SOLSPERSE24000, SOLSPERSE27000, SOLSPERSE28 000、 SOLSPERSE32500を利用することが出来る。本発明に用いられるアルカリ 可溶性高分子や、上述の (メタ)アクリル酸ベンジルを共重合したアルカリ可溶性高分 子およびその他アルカリ可溶性高分子も顔料分散剤としての機能を有する。分散剤 を含有する場合の含有量は 0. 1〜15質量％が好ましい。顔料の分散安定性の観点 力 0. 1%以上が好ましぐ密着性の観点から 15質量％以下が好ましい。より好まし くは 1〜10質量0 /0である。 [0078] Examples of the dispersant include carboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, Examples thereof include polysiloxanes, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) and a polyester having a free carboxylic acid group, and salts thereof. Further, a polymer dispersant having a basic functional group described in JP-A-2005-25169 can be used. Also, specifically, Disperbykl60, Disperbykl61, Disperby ykl62, Disperbykl63, Disperbvkl64, Disperbykl66 manufactured by Bicchem Corporation, and SOLSP manufactured by Geneca ERSE20000, SOLSPERSE24000, SOLSPERSE27000, SOLSPERSE28 000, SOLSPERSE32500 can be used. The alkali-soluble polymer used in the present invention, the alkali-soluble polymer copolymerized with the above-mentioned benzyl (meth) acrylate, and other alkali-soluble polymers also have a function as a pigment dispersant. The content in the case of containing a dispersant is preferably 0.1 to 15% by mass. From the viewpoint of adhesion, the power of 0.1% or more being preferred is preferably 15% by mass or less. More preferably rather is 1 to 10 mass 0/0.
[0079] さらに、ポリカルボン酸型高分子活性剤、ポリスルホン酸型高分子活性剤等のァ- オン性の活性剤、ポリオキシエチレン、ポリオキシレンブロックポリマー等のノ-オン系 の活性剤などは、前述の分散剤とともに分散助剤として用いることが出来る。  [0079] In addition, ion-active activators such as polycarboxylic acid type polymer activators and polysulfonic acid type polymer activators, and non-ionic activators such as polyoxyethylene and polyoxylene block polymers , And can be used as a dispersion aid together with the above-described dispersant.
[0080] また、黒色顔料とりわけカーボンブラックは、分散性、絶縁性等を考慮して、表面を 榭脂で被覆したり、榭脂ゃ低分子化合物で修飾したりできる。表面修飾に用いられる 榭脂としては、ポリカルポジイミド、エポキシ榭脂などカーボンブラック表面のカルボキ シル基と反応できる官能基を有する高分子が上げられる。同様に低分子化合物とし ては、例えば、置換ベンゼンジァゾ -ゥム化合物や置換ァリルジァゾ -ゥム化合物が 挙げられる。また、榭脂による被覆、修飾の方法としては、特開 2004— 219978号公 報、特開 2004— 217885号公報、特開 2004— 360723号公報、特開 2003— 201 381号公報、特開 2004— 292672号公報、特開 2004— 29745号公報、特開 200 5— 93965号公報、特開 2004— 4762号公報、米国特許 5, 554, 739号、米国特 許 5, 922, 118号に記載の分散剤、方法等を用いることができる。  [0080] In addition, black pigments, particularly carbon black, can be coated with a resin or modified with a low molecular weight compound in consideration of dispersibility, insulation, and the like. Examples of the resin used for the surface modification include polymers having a functional group capable of reacting with a carboxyl group on the surface of carbon black, such as polycarbopositimide and epoxy resin. Similarly, examples of the low molecular weight compound include substituted benzene diazo-um compounds and substituted aralkyl diazo-um compounds. Further, as a method of coating and modifying with rosin, JP 2004-219978 A, JP 2004-217885 A, JP 2004-360723 A, JP 2003-201 381, JP 2004 A — 292672, JP 2004-29745, JP 2005-93965, JP 2004-4762, U.S. Patent 5,554,739, U.S. Patent 5,922,118 The dispersant, method, etc. can be used.
[0081] 感光性榭脂組成物中には、光照射により発色する発色系染料を含有させることも できる。用いられる発色系染料としては、例えば、ロイコ染料又はフルオラン染料と、 ハロゲンィ匕合物の組み合わせがある。発色系染料は所望の OD値やカラー画素の色 純度に応じて適宜の量配合することができる。  [0081] The photosensitive resin composition may contain a coloring dye that develops color upon irradiation with light. Examples of the coloring dye used include a combination of a leuco dye or a fluoran dye and a halogen compound. The coloring dye can be blended in an appropriate amount depending on the desired OD value and color purity of the color pixel.
[0082] 上記ロイコ染料としては、例えば、トリス (4—ジメチルァミノ— 2—メチルフエ-ル)メ タン [ロイコクリスタルバイオレット]等が挙げられる。  [0082] Examples of the leuco dye include tris (4-dimethylamino-2-methylphenol) methane [leuco crystal violet].
[0083] 上記ハロゲン化合物としては、臭化ァミル、臭化イソァミル、臭ィ匕イソプチレン、臭化 エチレン、臭化ジフエ-ルメチル、臭化ベンザル、臭化メチレン、トリブロモメチルフエ ニノレスノレフォン、四臭化炭素、トリス（2, 3 ジブロモプロピル）ホスフェート、トリクロ口 ァセトアミド、ヨウ化ァミル、ヨウ化イソブチル、 1, 1, 1—トリクロ口— 2, 2—ビス（p ク ロロフエ-ル）ェタン、へキサクロロェタン、トリァジン化合物等が挙げられる。 [0083] Examples of the halogen compound include amyl bromide, isoamyl bromide, odorous isoprene, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethyl phenol. Ninoles norephone, carbon tetrabromide, tris (2,3 dibromopropyl) phosphate, trichloro-acetoamide, amyl iodide, isobutyl iodide, 1, 1, 1-triclo-ortho-2, 2-bis (p chlorophe- E) ethane, hexachloroethane, triazine compounds and the like.
[0084] 上記トリァジン化合物としては、 2, 4, 6 トリス（トリクロロメチル） s トリァジン、 2 [0084] Examples of the triazine compound include 2, 4, 6 tris (trichloromethyl) s triazine, 2
- (4—メトキシフエ-ル） 4、 6—ビス（トリクロロメチル） s トリァジンが挙げられる  -(4-methoxyphenol) 4, 6-bis (trichloromethyl) s triazine
[0085] このような発色系染料の中でも、トリブロモメチルフエ-ルスルフォンとロイコ染料と の組み合わせや、トリァジン化合物とロイコ染料との組み合わせが有用である。 [0085] Among such color developing dyes, combinations of tribromomethyl phenol sulfone and leuco dyes, and combinations of triazine compounds and leuco dyes are useful.
[0086] 感光性榭脂組成物中には、熱安定性や保存安定性を向上させるために、ラジカル 重合禁止剤を含有させることができる。このようなラジカル重合禁止剤としては、例え ば、 ρ—メトキシフエノール、ハイドロキノン、ピロガロール、ナフチルァミン、 tert—ブ チルカテコール、塩化第一銅、 2, 6—ジ—tert—ブチルー p クレゾール、 2, 2， 一 メチレンビス（4 ェチル 6— tert—ブチルフエノール）、 2, 2'—メチレンビス（4— メチルー 6— tert ブチルフエノール）、トリエチレングリコール ビス [3—（3—タ ーシヤリブチル 5—メチル 4—ヒドロキシフエ-ル）プロピオネート] (チバ'スぺシ ャルティ'ケミカルズ製 IRGANOX245)、ジフエ-ルニトロソァミン等が挙げられる。 感度低下が少ないことと保存安定性が良好であることとの両立から IRGANOX245 が好ましい。  [0086] The photosensitive resin composition may contain a radical polymerization inhibitor in order to improve thermal stability and storage stability. Examples of such radical polymerization inhibitors include ρ-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2, 6-di-tert-butyl-p-cresol, 2, 2 , 1 Methylene bis (4-ethyl 6-tert-butyl phenol), 2, 2'-methylene bis (4-methyl-6- tert butyl phenol), triethylene glycol bis [3- (3-tert-butyl 5-methyl 4-hydroxy phenol] -Le) propionate] (IRGANOX245 manufactured by Ciba 'Specialty' Chemicals), diphenylnitrosamine and the like. IRGANOX245 is preferred because it is compatible with low sensitivity reduction and good storage stability.
[0087] 感光性榭脂組成物中には、必要に応じて可塑剤を含有させることもできる。そのよう な可塑剤としては、フタル酸エステル類、例えば、ジェチルフタレートや、 p—トルエン スルホンアミド、ポリプロピレングリコール、ポリエチレングリコールモノアルキルエーテ ル、ポリアルキレンォキシド変性ビスフエノール A誘導体、例えば、ビスフエノール Aの エチレンォキシド付加物やプロピレンォキシド付加物が挙げられる。可塑剤を含有す る場合の好ましい量は 0. 1〜5質量％である。感光性榭脂層の可とう性およびラミネ ート後の切断時にチップ飛びや割れなどを抑制する観点力 0. 1質量％以上が好ま しぐ密着性の観点から 5質量％以下が好ましい。  [0087] In the photosensitive resin composition, a plasticizer may be contained as necessary. Examples of such plasticizers include phthalates such as jetyl phthalate, p-toluenesulfonamide, polypropylene glycol, polyethylene glycol monoalkyl ether, polyalkyleneoxide-modified bisphenol A derivatives such as bisphenol. Examples include an ethylene oxide adduct and propylene oxide adduct of A. A preferable amount when the plasticizer is contained is 0.1 to 5% by mass. In view of the flexibility of the photosensitive resin layer and the viewpoint power to suppress chip jumping and cracking at the time of cutting after lamination, 0.1% by mass or more is preferable, and 5% by mass or less is preferable.
[0088] 感光性榭脂組成物中には、シランカップリング剤を含むことが出来る。シランカップ リング剤としては、ビニル基、エポキシ基、スチリル基、メタクリロキシ基、アタリロキシ 基、アミノ基、ウレイド基、クロ口プロピル基、メルカプト基、スルフイド基、イソシァネー ト基、イミダゾリル基などの極性基と、アルコキシシリル基とを分子内に有する化合物 などを上げることが出来る。具体的には、信越シリコーン (株)製、 KBM— 1003、 KB E— 1003、 KBM— 403、 KBE— 403、 KBM— 502、 KBE— 502、 KBM— 503、 KBE— 503、 KBM— 603、 KBE— 603、 KBM— 903、 KBE— 903、 KBE— 585 、 KBM— 802、 KBE— 846、 KBE— 9007などや、特開 2004— 280057号公報に 記載のイミダゾールシランィ匕合物などを挙げることが出来る。配合量は、密着性の効 果と現像後の基板への残渣の付着などを考慮して適宜選択できるが、 0. 01〜1質 量％の範囲で含むことが好まし 、。 [0088] The photosensitive resin composition may contain a silane coupling agent. Silane coupling agents include vinyl, epoxy, styryl, methacryloxy, and attaryloxy. And compounds having a polar group such as a group, amino group, ureido group, black propyl group, mercapto group, sulfide group, isocyanate group, imidazolyl group, and alkoxysilyl group in the molecule. Specifically, Shin-Etsu Silicone Co., Ltd., KBM-1003, KB E-1003, KBM-403, KBE-403, KBM-502, KBE-502, KBM-503, KBE-503, KBM-603, KBE — 603, KBM-903, KBE-903, KBE-585, KBM-802, KBE-846, KBE-9007, and the imidazolesilane compound described in JP-A-2004-280057. I can do it. The blending amount can be appropriately selected in consideration of the effect of adhesion and the adhesion of residues to the substrate after development, but it is preferable to include it in the range of 0.01 to 1% by mass.
[0089] 本発明の感光性榭脂積層体は、感光性榭脂組成物カゝらなる感光性榭脂層を支持 層上に塗工して作製することが出来る。ここで用いられる支持層としては、活性光を 透過する透明なものが好ましい。活性光を透過する支持層としては、ポリエチレンテ レフタレ トフイルム、ポリビュルアルコールフィルム、ポリ塩化ビュルフィルム、塩化 ビニル共重合体フィルム、ポリ塩ィヒビユリデンフィルム、塩化ビ-リデン共重合体フィ ルム、ポリメタクリル酸メチル共重合体フィルム、ポリスチレンフィルム、ポリアクリロ-ト リルフィルム、スチレン共重合体フィルム、ポリアミドフィルム、セルロース誘導体フィル ム、トリァセチルセルロースフィルム、ポリプロピレンフィルム等が挙げられる。これらの フィルムとしては、必要に応じ延伸されたものも使用可能である。  [0089] The photosensitive resin laminate of the present invention can be produced by coating a photosensitive resin layer comprising a photosensitive resin composition on a support layer. The support layer used here is preferably a transparent layer that transmits active light. Examples of the support layer that transmits active light include polyethylene terephthalate film, polybutyl alcohol film, polybutyl alcohol film, vinyl chloride copolymer film, polyvinyl chloride film, polyvinylidene chloride copolymer film, Examples include polymethyl methacrylate copolymer film, polystyrene film, polyacrylo-tril film, styrene copolymer film, polyamide film, cellulose derivative film, triacetyl cellulose film, and polypropylene film. As these films, those stretched as necessary can be used.
[0090] また、支持層に塗工する際には適宜溶媒を加えて塗工に最適な状態に整えること が出来る。溶媒としては、例えば、エチレングリコールモノメチルエーテル、エチレン グリコーノレモノェチノレエーテノレ、エチレングリコーノレモノプロピノレエーテノレ、エチレン グリコールモノブチルエーテル、エチレングリコールジメチルエーテル、エチレングリ コーノレジェチノレエーテノレ、エチレングリコーノレジブ口ピノレエーテノレ、プロピレングリコ 一ノレモノメチノレエーテノレ、プロピレングリコーノレモノェチノレエーテノレ、プロピレングリコ ールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、プロピレング リコールジメチルエーテル、プロピレングリコールジェチルエーテル、ジエチレングリ コーノレモノメチノレエーテノレ、ジエチレングリコーノレモノェチノレエーテノレ、ジエチレング リコーノレジメチノレエーテノレ、ジエチレングリコーノレジェチノレエーテノレ-エチレングリコ 一ノレモノメチノレエーテノレアセテート、エチレングリコーノレモノェチノレエーテノレァセテ ート、エチレングリコールモノプロピルエーテルアセテート、エチレングリコーノレモノブ チノレエーテノレアセテート、プロピレングリコーノレモノメチノレエーテノレアセテート（PGM EA)、プロピレングリコーノレモノェチノレエーテノレアセテート、プロピレングリコーノレモノ プロピルエーテルアセテート、 2—メトキシブチルアセテート、 3—メトキシブチルァセ テート、 4ーメトキシブチルアセテート、 2—メチルー 3—メトキシブチルアセテート、 3 ーメチルー 3—メトキシブチルアセテート、 3—ェチルー 3—メトキシブチルアセテート 、 2 ェトキシブチノレアセテート、 4ーェトキシブチノレアセテート、 4 プロポキシブチ ルアセテート、 2—メトキシペンチルアセテート、 3—メトキシペンチルアセテート、 4 メトキシペンチルアセテート、 2—メチルー 3—メトキシペンチルアセテート、 3 メチル 3—メトキシペンチルアセテート、 3—メチルー 4ーメトキシペンチルアセテート、 4 メチルー 4ーメトキシペンチルアセテート、アセトン、メチルェチルケトン、ジェチルケト ン、メチルシソブチルケトン、ェチルイソブチルケトン、炭酸メチル、炭酸ェチル、炭酸 プロピル、炭酸ブチル、ベンゼン、トルエン、キシレン、シクロへキサノン、メタノール、 エタノーノレ、プロパノーノレ、ブタノーノレ、へキサノーノレ、シクロへキサノーノレ、エチレン グリコール、ジエチレングリコール、グリセリンが挙げられる。毒性、支持層に塗工した 際の乾燥性の観点からメチルェチルケトンやメチルイソプチルケトンが好ましぐ着色 顔料とくに黒色顔料の分散安定性や本発明に用いられる上記式 (I)で表されるアル カリ可溶性高分子の溶解性の観点カゝらプロピレングリコールモノメチルエーテルァセ テート (PGMEA)が好まし 、。前記の性能を両立するためにメチルェチルケトンゃメ チルイソブチルケトンなどと PGMEAとを適当な割合で混合して用いても良 ヽ。例え ば、黒色顔料を予め分散させた PGMEA、上記式 (I)のアルカリ可溶性高分子を予 め溶解させた PGMEA、それぞれと上述した重量平均分子量が 3, 000〜100, 00 0であるメタクリル酸べンジル又はアクリル酸ベンジルを共重合したアルカリ可溶性高 分子及び重量平均分子量が 3, 000〜50, 000であるアクリル系のアルカリ可溶性 高分子力もなる群より選ばれる少なくとも一種のアルカリ可溶性高分子、エチレン性 不飽和二重結合を有する光重合性化合物、光重合開始剤、その他の種々の添加物 を混合してメチルェチルケトンや PGMEAなどの溶媒で適宜希釈し、支持層への塗 布性乾燥性の良好な感光性榭脂組成物溶液として調合することが出来る。 [0090] Further, when coating on the support layer, an appropriate solvent can be added to adjust the coating layer to an optimum state. Solvents include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl enoate ethere, ethylene glycol monomono propenoate ethere, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl etherenole, ethylene glycol Norési mouth pinoleatenore, propylene glycol monoremonomethinoleatenore, propyleneglycolenoremonoethylenoatere, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol jetyl ether, diethylene glycol Cornole Monomethinoreatenore, Diethylene Glycole Monolechinenoreatenore, Diethylene Glicono-resin methinoleatenore, diethyleneglycoleno retinoatenore-ethyleneglycol Monoremonomethylenoatenoreacetate, Ethylene glycol monorenoatenoateoate acetate, Ethylene glycol monopropyl ether acetate, Ethylene glycol monolebutinoatenoate acetate, Propylene glycolino monomethinoatenoate acetate (PGM EA), propylene glycol monoethanolinoate acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxy Butyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethylbutyl 3-methoxybutyl acetate, 2-ethybutynoacetate, 4-etoxybutynoacetate, 4 propoxybutyral Cetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl 3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxy Pentyl acetate, acetone, methyl ethyl ketone, jetyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, benzene, toluene, xylene, cyclohexanone, methanol, ethanol, propanol , Butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin. Methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoint of toxicity and drying properties when applied to the support layer. Coloring pigments, particularly the dispersion stability of black pigments, and the above formula (I) used in the present invention. In view of the solubility of the alkali-soluble polymer, propylene glycol monomethyl etherate (PGMEA) is preferred. In order to achieve both of the above performances, methyl ethyl ketone, methyl isobutyl ketone, etc. and PGMEA may be mixed at an appropriate ratio. For example, PGMEA in which a black pigment is preliminarily dispersed, PGMEA in which an alkali-soluble polymer of the above formula (I) is preliminarily dissolved, and methacrylic acid having a weight average molecular weight of 3,000 to 100,000 and 00, respectively. An alkali-soluble polymer copolymerized with benzyl or benzyl acrylate, and at least one alkali-soluble polymer selected from the group consisting of an acrylic alkali-soluble polymer having a weight average molecular weight of 3,000 to 50,000, which also has a high molecular force, ethylene A photopolymerizable compound having an unsaturated double bond, a photopolymerization initiator, and other various additives are mixed and appropriately diluted with a solvent such as methyl ethyl ketone or PGMEA, and applied to the support layer. It can be prepared as a photosensitive resin composition solution having good fabric drying properties.
[0091] また、上記支持層のヘーズは 5. 0以下であるものが好ましい。より好ましくは 2. 0以 下、更に好ましくは 1. 0以下である。ここでいうヘーズ (Haze)とは濁度を表す値であ り、ランプにより照射され試料中を透過した全透過率 Tと、試料中で拡散され散乱し た光の透過率 Dにより、ヘーズ値 H = DZTX 100として求められる。これら ίお IS— K— 7105により規定されており、市販の濁度計によって容易に測定可能である。支 持層の厚みは薄い方が画像形成性、経済性の面で有利である力 強度を維持する 必要から、 10〜100 /ζ πιのものが一般的である。 [0091] The haze of the support layer is preferably 5.0 or less. More preferably, it is 2.0 or less, and more preferably 1.0 or less. Haze as used herein is a value representing turbidity, and the haze value is determined by the total transmittance T irradiated through the lamp and transmitted through the sample and the transmittance D of light diffused and scattered in the sample. Calculated as H = DZTX 100. These standards are defined by IS-K-7105 and can be easily measured with a commercially available turbidimeter. The thickness of the support layer is generally 10 to 100 / ζ πι because it is necessary to maintain the strength and strength, which is advantageous in terms of image forming property and economical efficiency.
[0092] 本発明の感光性榭脂積層体は、感光性榭脂層の支持層とは反対側の表面に、必 要に応じて保護層を積層することも出来る。支持層と感光性榭脂層との密着力よりも 、保護層と感光性榭脂層との密着力が充分小さぐ容易に剥離できることが好ましい 。このような保護層としては、例えば、ポリエチレンフィルム、ポリエチレンテレフタレー トフイルム、ポリプロピレンフィルム、延伸ポリプロピレンフィルム（例えば、王子製紙（ 株）製 Ε— 200C、 E— 200Aなど）、離型処理されたポエチレンテレフタレートフィル ム等が挙げられる。保護層の好ましい厚みは、 15〜50 /ζ πιである。表面平滑製の観 点から 15 m以上が好ましぐ感光性榭脂層との積層性、巻き取り性の観点から 50 /z m以下が好ましい。 [0092] In the photosensitive resin laminate of the present invention, a protective layer can be laminated on the surface of the photosensitive resin layer opposite to the support layer, if necessary. It is preferable that the adhesive force between the protective layer and the photosensitive resin layer is sufficiently smaller than the adhesive force between the support layer and the photosensitive resin layer, and it can be easily peeled off. Examples of such a protective layer include polyethylene film, polyethylene terephthalate film, polypropylene film, stretched polypropylene film (for example, Oji Paper Co., Ltd. Ε-200C, E-200A, etc.), and release-treated polyethylene. Examples include terephthalate film. The preferred thickness of the protective layer is 15-50 / ζ πι. From the viewpoint of smooth surface production, a thickness of 15 m or more is preferable, and from the viewpoint of lamination with a photosensitive resin layer and winding property, 50 / z m or less is preferable.
[0093] 本発明の感光性榭脂積層体は、おおよそ次のような手法で作製することが出来る。  [0093] The photosensitive resin laminate of the present invention can be prepared by the following method.
感光性榭脂組成物として、アルカリ可溶性高分子、エチレン性不飽和二重結合を有 する光重合性化合物、光重合開始剤、着色顔料等を、粘度力 ^〜数十 cpsになるよう な適量の溶媒と共に混合して、感光性榭脂組成物溶液を作製する。支持層となる厚 み 20 μ mの透明ポリエステルフィルムの上に上記感光性榭脂組成物溶液を塗布し て乾燥し、感光性榭脂層を形成する。塗布は、塗布面積や塗布速度などに応じた装 置を用いて塗布する。塗布装置としては、小面積に有用なものとして、ブレードコータ 一、バーコ一ター、グラビアコーターを挙げることができる。密封式ダイ方式であれば 、キヤピラリ 1 ~~コ1 ~~タ' ~~ レイジングアンドライジングコ ~~タ' ~~、スロットダイコ1 ~~タ' ~" リ ップコ一ター、開放式であれば、コンマコーター、グラビアコーターを挙げることが出 来る。乾燥温度は、溶剤に応じて適宜選定することが出来る。溶剤を十分に乾燥させ る温度以上が好ましぐ支持層の寸法安定性が確保できる温度以下で乾燥すること が好ましい。 60〜120°Cが好ましい。乾燥時間は、溶剤が十分に乾燥できる程度以 上に長ぐまた溶剤を塗布面力 均質に蒸発させることが出来る程度の速度で乾燥さ せることが好ましい。支持層の寸法安定性が確保でき無くならない程度、さらに作業 性が著しく損なわれない程度以下であることが好ましい。乾燥手段は、小面積であれ ばキャスト法や熱風循環式乾燥炉を用いることが出来る。数メートル以上の乾燥チヤ ンバーを通過して乾燥させるには、熱風を塗布面や支持層に吹き付けたり、加熱され たロールの上支持層を通過させることにより乾燥させることができる。熱風ノズルにはAs a photosensitive resin composition, an appropriate amount of an alkali-soluble polymer, a photopolymerizable compound having an ethylenically unsaturated double bond, a photopolymerization initiator, a color pigment, etc., so as to have a viscosity power of ^ to several tens cps A photosensitive resin composition solution is prepared by mixing with the above solvent. The photosensitive resin composition solution is applied onto a 20 μm thick transparent polyester film to be a support layer and dried to form a photosensitive resin layer. Application is performed using an apparatus according to the application area, application speed, and the like. Examples of the coating apparatus include a blade coater, a bar coater, and a gravure coater that are useful for a small area. If it is a sealed die method, Capillary 1 ~~ Co 1 ~~ Ta '~~ Raging and Rising Co ~~ Ta' ~~, Slot Daiko 1 ~~ Ta '~ "Rip Collector, Open Type Comb coaters and gravure coaters can be selected, and the drying temperature can be selected appropriately according to the solvent. It is preferable to dry at a temperature not higher than the temperature at which the dimensional stability of the support layer can be secured. 60-120 ° C is preferred. It is preferable that the drying time is longer than the degree at which the solvent can be sufficiently dried and the solvent is dried at a speed at which the applied surface force can be evaporated uniformly. It is preferable that the dimensional stability of the support layer is not more than the extent that the dimensional stability cannot be ensured and the workability is not significantly impaired. If the drying means is a small area, a casting method or a hot-air circulating drying furnace can be used. In order to dry it through a drying chamber of several meters or more, it can be dried by blowing hot air on the coated surface or the supporting layer, or by passing it through the upper supporting layer of a heated roll. Hot air nozzle
、ジェット型、正圧エアーフローティング型、負圧エアーフローティング型、負圧ノズル +ロール型、パンチング穴型、平行流型などがある。その後で保護層となるポリェチ レンフィルムを貼り合わせて積層する。ブラックマトリックスの遮光性と塗布時の膜厚 精度から、感光性榭脂層の厚みは 0. 3 m以上であることが好ましい。また、カラー フィルタに用いたときの平坦性から、 4. 5 /z m以下であることが好ましい。榭脂ブラッ クマトリックスを用いてカラーフィルタを作成する場合、ブラックマトリックスの高さが高 いとカラーフィルタの表面の凹凸が液晶の配向を乱すので、オーバーコート層とよば れる平坦ィ匕膜を設けたり、表面を平らにするために研磨したりする場合がある。液晶 の配向への影響を小さくしたり、オーバーコート層を薄くしたり、カラーフィルタ全体の 厚みを薄くしたりできるので、ブラックマトリックスの高さは 4. 5 m以下であることが 好ましい。感光性榭脂層の厚みは、より好ましくは 0. 3〜2 111、更に好ましくは0. 3 〜0. 8 mである。 , Jet type, positive pressure air floating type, negative pressure air floating type, negative pressure nozzle + roll type, punching hole type, parallel flow type, etc. After that, a polyethylene film to be a protective layer is laminated and laminated. The thickness of the photosensitive resin layer is preferably 0.3 m or more from the light shielding property of the black matrix and the film thickness accuracy during coating. Moreover, it is preferable that it is 4.5 / zm or less from the flatness when it is used for a color filter. When creating a color filter using a resin black matrix, if the height of the black matrix is high, the unevenness of the surface of the color filter disturbs the alignment of the liquid crystal, so a flat film called an overcoat layer is provided. Or polishing to flatten the surface. The height of the black matrix is preferably 4.5 m or less because the influence on the orientation of the liquid crystal can be reduced, the overcoat layer can be thinned, and the overall thickness of the color filter can be reduced. The thickness of the photosensitive resin layer is more preferably 0.3 to 2111, and still more preferably 0.3 to 0.8 m.
[0094] 本発明に記載のブラックマトリックスは上記の感光性榭脂積層体を用いておおよそ 次のような手法で形成することが出来る。まず保護層を剥離した後、ガラス基板に上 記感光性榭脂積層体をラミネート (熱圧着)する。このとき、ガラス基板は予熱されるこ とが好ましい。ガラス基板の予熱温度は、ラミネート性およびラミネート時に巻き込む 空気を抑制し十分な密着性を確保する観点から 100°C以上が好ましぐ支持層の耐 熱性の観点から 150°C以下が好ましい。より好ましくは 110°C以上 140°C以下である  [0094] The black matrix described in the present invention can be formed by the following method using the above-described photosensitive resin laminate. First, after removing the protective layer, the above photosensitive resin laminate is laminated (thermocompression bonding) on a glass substrate. At this time, the glass substrate is preferably preheated. The preheating temperature of the glass substrate is preferably 150 ° C. or lower from the viewpoint of laminating properties and the heat resistance of the support layer, which is preferably 100 ° C. or higher from the viewpoint of suppressing air entrained during lamination and ensuring sufficient adhesion. More preferably, it is 110 ° C or higher and 140 ° C or lower
[0095] 次に、マスクフィルムを通して活性光により画像露光する。露光量を上げて露光す る場合は、露光前に支持層を剥離しても良い。但し、支持層を剥離して露光する場 合は、開始剤の配合量や本発明に含まれる上記式 (I)で表される化合物の配合量な どを適宜調整して、高感度に設計することが好ましい。感度に対する支持層の影響 は大きぐ支持層を介して露光する場合とくらべて非常に高感度に設計することが好 ましい。即ち、本発明の（1)〜（7)に記載の感光性榭脂積層体において光重合開始 剤を 8〜20質量％含む感光性榭脂積層体を、基板にラミネートする工程、支持層を 剥離する工程、露光する工程、現像する工程を順に行うことを特徴とするブラックマト リックス付き基板の製造方法により、ブラックマトリックスを製造することが好ましい。基 板としては、透明基板、例えばガラス基板が好ましい。前記製造方法においては、ェ 程上露光部が支持層に貼り付き基材力 剥離してしまう転写性の問題が回避される ので、感光性榭脂組成物中の上述した重量平均分子量が 3, 000-100, 000であ るメタクリル酸べンジル又はアクリル酸ベンジルを共重合したアルカリ可溶性高分子 及び重量平均分子量が 3, 000〜50, 000であるアクリル系のアルカリ可溶性高分 子カゝらなる群より選ばれる少なくとも一種のアルカリ可溶性高分子の配合比率を低く 抑え、上記式 (I)で表される化合物の配合量を多くすることが出来る。これは、感度の 観点から好ましい。しかし、前記製造方法であっても未露光部が支持層に強く粘着 するため、重量平均分子量が 3, 000〜100, 000であるメタクリル酸べンジル又はァ クリル酸ベンジルを共重合したアルカリ可溶性高分子及び重量平均分子量が 3, 00 0-50, 000であるアクリル系のアルカリ可溶性高分子力 なる群より選ばれる少なく とも一種のアルカリ可溶性高分子の配合比率は 1質量％以上であり、感度の観点か ら 40質量％以下である。好ましくは 1〜15質量％であり、より好ましくは 1〜10質量 %であり、更に好ましくは 1〜5質量％である。また、同様に、未露光部が支持層に強 く粘着するため、上記式 (I)で表される化合物の配合量は 40質量％以下であり、感 度の観点から 3質量％以上である。好ましくは 10〜40質量％であり、より好ましくは 1 5〜40質量％であり、更に好ましくは 20〜40質量％である。 Next, image exposure is performed with active light through a mask film. Increase exposure and expose In this case, the support layer may be peeled off before exposure. However, when the support layer is peeled off and exposed, the amount of the initiator and the amount of the compound represented by the above formula (I) included in the present invention are appropriately adjusted to design with high sensitivity. It is preferable to do. The effect of the support layer on the sensitivity is preferably designed to be very sensitive compared to exposure through a large support layer. That is, in the photosensitive resin laminate according to (1) to (7) of the present invention, a step of laminating a photosensitive resin laminate containing 8 to 20% by mass of a photopolymerization initiator on a substrate, a support layer It is preferable to manufacture a black matrix by a method for manufacturing a substrate with a black matrix, which is characterized by sequentially performing a peeling step, an exposing step, and a developing step. As the substrate, a transparent substrate such as a glass substrate is preferable. In the above production method, the above-mentioned weight average molecular weight in the photosensitive resin composition is 3, since the problem of transferability where the exposed portion sticks to the support layer and the substrate force peels off is avoided. An alkali-soluble polymer copolymerized with benzyl methacrylate or benzyl acrylate that is 000-100, 000 and an acrylic alkali-soluble polymer that has a weight average molecular weight of 3,000 to 50,000 The compounding ratio of at least one alkali-soluble polymer selected from the group can be kept low, and the compounding amount of the compound represented by the above formula (I) can be increased. This is preferable from the viewpoint of sensitivity. However, even in the production method described above, the unexposed area strongly adheres to the support layer, so that an alkali-soluble highly copolymerized benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000. The blending ratio of at least one alkali-soluble polymer selected from the group consisting of acrylic alkali-soluble polymers having a molecular weight and a weight average molecular weight of 3,00 0-50,000 is 1% by mass or more. From the viewpoint, it is 40% by mass or less. Preferably it is 1-15 mass%, More preferably, it is 1-10 mass%, More preferably, it is 1-5 mass%. Similarly, since the unexposed portion strongly adheres to the support layer, the compounding amount of the compound represented by the formula (I) is 40% by mass or less, and 3% by mass or more from the viewpoint of sensitivity. . Preferably it is 10-40 mass%, More preferably, it is 15-40 mass%, More preferably, it is 20-40 mass%.
次に、感光性榭脂層上に支持層がある場合には、必要に応じてこれを除き、続い てアルカリ水溶液を用いて未露光部の感光性榭脂層を現像し、除去する。アルカリ 水溶液としては、炭酸ナトリウム水溶液、炭酸カリウム水溶液、水酸化カリウム水溶液 、炭酸水素ナトリウムと炭酸ナトリウムの混合水溶液、テトラメチルアンモ-ゥムヒドロキ シドなどの有機アミン水溶液等を用いる。これらのアルカリ水溶液は感光性榭脂層の 特性に合わせて選択される。一般的に 0. 1〜3質量％の炭酸ナトリウム水溶液、 0. 0 3〜0. 1質量％の水酸化カリウム水溶液が用いられる。必要に応じて、現像しきれず に残って!/ヽる光重合性榭脂層を取り除くために、別の現像液にぉ ヽて更に現像を行 つても良い。別の現像液とは、初めに感光性榭脂層を現像する際に用いる現像液と はアルカリ性の異なるアルカリ水溶液であったり、酸性現像液であったり、有機溶剤を 含有する現像液であったりしてもよぐ現像液に合わせて感光性榭脂層の組成を適 宜選ぶことが出来る。また、現像しきれずに残っている未露光部の感光性榭脂層や、 着色顔料、黒色顔料は、高圧水洗などの方法により物理的に除去することも出来る。 0. 2MPa以上の水洗圧が効果的である。 Next, when there is a support layer on the photosensitive resin layer, this is removed as necessary, and then the photosensitive resin layer in the unexposed area is developed and removed using an alkaline aqueous solution. Examples of alkaline aqueous solutions include sodium carbonate aqueous solution, potassium carbonate aqueous solution, and potassium hydroxide aqueous solution. Use a mixed aqueous solution of sodium hydrogen carbonate and sodium carbonate, an aqueous organic amine solution such as tetramethyl ammonium hydroxide, and the like. These alkaline aqueous solutions are selected according to the characteristics of the photosensitive resin layer. In general, a 0.1 to 3% by weight aqueous sodium carbonate solution and a 0.03 to 0.1% by weight aqueous potassium hydroxide solution are used. If necessary, in order to remove the photopolymerizable resin layer that remains without being fully developed, it may be further developed in another developer. Another developer is an alkaline aqueous solution having a different alkalinity from the developer used when first developing the photosensitive resin layer, an acidic developer, or a developer containing an organic solvent. However, the composition of the photosensitive resin layer can be appropriately selected according to the developer. Further, the photosensitive resin layer in the unexposed area remaining undeveloped, the colored pigment, and the black pigment can be physically removed by a method such as high pressure water washing. 0. A washing pressure of 2 MPa or more is effective.
[0097] 本発明のカラーフィルタは、ブラックマトリックスを形成後、該ブラックマトリックス付き ガラス基板の少なくともブラックマトリックスで覆われて ヽな 、部分の一部に、本発明 の感光性榭脂積層体ゃ感熱性または感光性のカラーインクによって、赤 ·青 ·緑の力 ラー画素を形成することによって作製できる。  [0097] After forming the black matrix, the color filter of the present invention is covered with at least the black matrix of the glass substrate with the black matrix. It can be produced by forming red, blue, and green power pixels with a photosensitive or photosensitive color ink.
[0098] ブラックマトリックスの形状はカラー画素を囲む格子状のものが一般的である。また 、格子の各辺のパターン幅は 5〜50 μ m、格子点間隔は 30〜500 μ mであるのが 一般的である。  The shape of the black matrix is generally a lattice shape surrounding the color pixels. In general, the pattern width of each side of the lattice is 5 to 50 μm, and the interval between lattice points is 30 to 500 μm.
[0099] 赤 '青'緑のカラー画素は、本発明の感光性榭脂積層体や液状レジストなどのカラ 一レジストを用いたフォトリソグラフィ一によつて作製したり、カラーインクを用いたイン クジェット法、印刷法などによって作製したり、種々の方法を用いることが出来る。イン クジェット法とは、ガラス基板上に形成されたブラックマトリックスを堰として、インクジェ ット方式でカラーインクを注入する方法である。インクジェット法は、高価なマスクを必 要とする露光工程を必要としない、現像工程を必要としない、凹凸にかかわらず画素 ノ ターンを形成できる、歩留まりが向上する、などの面から、低コストで簡便に画素パ ターンを形成できるので好ましい。フォトリソグラフィーによらずに硬化できるので感熱 性でも良いし、全面露光によって硬化させることもできるので感光性であっても良い。 感熱性または感光性のカラーインクとしては公知のものも用いることが出来る。また、 本発明において、着色物質として例示した顔料および染料、エチレン性不飽和二重 結合を有する光重合性化合物、熱または光重合性開始剤とを有し、溶剤により粘度 を適宜調整した組成物を用いることが出来る。例えば特開 2004— 213033号公報 の実施例 1に記載の着色インクなどを用いることが出来る。また、ブラックマトリックス は撥カラーインク性であることが好ましい。この性質によりインクの着弾精度の問題か らブラックマトリックス上に乗ったカラーインクも堰を滑り落ちてカラー画素用の空間を 満たすことが出来る。 [0099] The red 'blue' and green color pixels are produced by photolithography using a color resist such as the photosensitive resin laminate or liquid resist of the present invention, or ink jets using color inks. It can be produced by a method or a printing method, or various methods can be used. The ink jet method is a method of injecting color ink by an ink jet method using a black matrix formed on a glass substrate as a weir. The inkjet method does not require an exposure process that requires an expensive mask, does not require a development process, can form a pixel pattern regardless of unevenness, and improves the yield. This is preferable because a pixel pattern can be easily formed. Since it can be cured without using photolithography, it may be heat-sensitive, or it may be photo-sensitive because it can be cured by overall exposure. Known heat-sensitive or photosensitive color inks can also be used. Also, In the present invention, a composition having a pigment and a dye exemplified as a coloring substance, a photopolymerizable compound having an ethylenically unsaturated double bond, a heat or a photopolymerizable initiator, and having a viscosity adjusted appropriately with a solvent is used. I can do it. For example, the colored ink described in Example 1 of JP-A-2004-213033 can be used. The black matrix is preferably color repellent ink. Due to this property, due to the problem of ink landing accuracy, the color ink on the black matrix can also slide down the weir to fill the space for the color pixels.
[0100] 本発明のブラックマトリックスの製造方法においては、透明な支持層に積層した感 光性榭脂積層体を使用する。該製造方法は、感光性榭脂組成物をガラス基板に直 接塗布して乾燥し、後にフォトマスクを通して露光し現像する製造方法と比較して、乾 燥工程を使用しない、ガラスに塗布する際の膜厚ムラが生じない、透明な支持層が 光重合性榭脂組成物とフォトマスクとの接触を防 、で 、るのでフォトマスクが汚れにく い、などの面で好ましい手法である。  [0100] In the method for producing a black matrix of the present invention, a photosensitive resin laminate laminated on a transparent support layer is used. In the production method, the photosensitive resin composition is applied directly to a glass substrate, dried, and then exposed to development through a photomask, and then applied to glass without using a drying step. This is a preferable method in that the film thickness non-uniformity does not occur and the transparent support layer prevents contact between the photopolymerizable resin composition and the photomask, so that the photomask is not easily contaminated.
[0101] さらに、透明な支持層を介して露光することにより、感光性榭脂層が直接酸素と接 触することを防ぐため非常に高い感度が得られる。これは、特許文献 1、本願明細書 比較例 8などに開示されているようなガラス基板に感光性榭脂組成物を直接塗布乾 燥する方法と比較して、感度の点で有用であることを示して 、る。  [0101] Further, by exposing through a transparent support layer, the photosensitive resin layer is prevented from coming into direct contact with oxygen, so that a very high sensitivity can be obtained. This is useful in terms of sensitivity as compared with a method in which a photosensitive resin composition is directly applied and dried on a glass substrate as disclosed in Patent Document 1, Comparative Example 8 of the present specification and the like. Showing
[0102] 感光性榭脂積層体を用いてブラックマトリックスを作成する方法としては、厚み約 2 mのカラー画素をガラス基板上に形成した後に黒色の感光性榭脂積層体をカラー 画素付きガラス基板に積層し、ガラス基板側力 露光する方法も従来力 知られて ヽ る（特許 3409925号公報参照)。この順序でブラックマトリックスを形成すると、もとも と画素の間にしかブラックマトリックスが形成されないので、カラー画素とブラックマトリ ッタスの位置合わせが省略できる利点がある。しかし、このような方法では、カラー画 素間に感光性榭脂層を埋め込むために、 70ないし 100 m以上の厚みをもった支 持層に熱可塑性榭脂層および中間層を積層し、さらに感光性榭脂層を積層するとい つた複雑な層構造になる。熱可塑性榭脂層は埋め込み性のために、中間層は厚くな つた支持層および Zまたは熱可塑性榭脂層を剥離した後に露光する際感光性榭脂 層と酸素との接触を防ぐために設けられると考えられる。本発明の感光性榭脂積層 体を用いれば、線幅再現性、密着性にすぐれるので先行してブラックマトリックスを形 成することが可能で、そのため層構造も単純ィ匕され、支持層も 20 m以下の露光波 長の吸収散乱が少ないものを用いることが出来る。高品位の支持層を用いることでさ らに線幅安定性やパターンの形状、直線性などが向上する。 [0102] As a method of forming a black matrix using a photosensitive resin laminate, a black photosensitive resin laminate is formed on a glass substrate after color pixels having a thickness of about 2 m are formed on the glass substrate. Conventionally, a method of laminating the film and exposing the glass substrate side force is also known (see Japanese Patent No. 3409925). Forming the black matrix in this order has the advantage that the black matrix is originally formed only between the pixels, so that the alignment of the color pixels and the black matrix can be omitted. However, in such a method, in order to embed a photosensitive resin layer between color pixels, a thermoplastic resin layer and an intermediate layer are laminated on a support layer having a thickness of 70 to 100 m or more, and further, Laminating a photosensitive resin layer results in a complex layer structure. The thermoplastic resin layer is embedded for embedding, and the intermediate layer is provided to prevent contact between the thickened support layer and the Z or thermoplastic resin layer after exposure after peeling the photosensitive resin layer and oxygen. it is conceivable that. Photosensitive resin laminate of the present invention By using a body, it is possible to form a black matrix in advance because it has excellent line width reproducibility and adhesion, so that the layer structure is simplified and the support layer has an exposure wavelength of 20 m or less. A thing with little absorption scattering can be used. By using a high-quality support layer, line width stability, pattern shape, and linearity are further improved.
実施例  Example
[0103] 本発明を実施例に基づいて説明する。  The present invention will be described based on examples.
[合成例 1]  [Synthesis Example 1]
まず、特開 2001— 354735号公報に記載の方法に従って上記式 (I)で表される化 合物 1を合成した。  First, Compound 1 represented by the above formula (I) was synthesized according to the method described in JP-A-2001-354735.
すなわち、 500ml四つ口フラスコ中に、ビスフエノールフルオレン型エポキシ榭脂 23 5g (エポキシ当量 235)とテトラメチルアンモ -ゥムクロライド 110mg、 2, 6—ジ一 tert ブチル—4—メチルフエノール lOOmg及びアクリル酸 72. Ogを仕込んだ。これに 25 mlZ分の速度で空気を吹き込みながら 90〜100°Cで加熱溶解した。次ぎに、溶液 が白濁した状態のまま徐々に昇温し、 120°Cに加熱して完全溶解させた。ここで溶液 は次第に透明粘稠になったがそのまま撹拌を継続した。この間、酸価を測定し、 1. 0 mgKOHZg未満になるまで加熱撹拌を続けた。酸価が目標に達するまで 12時間を 要した。そして室温まで冷却し、無色透明で固体状の下記式 (V)で表されるビスフ ノールフルオレン型エポキシアタリレートを得た。  That is, in a 500 ml four-necked flask, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 2,6-ditert-butyl-4-methylphenol lOOmg and acrylic acid 72 Og was charged. This was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 mlZ. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C to be completely dissolved. Here, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOHZg. It took 12 hours for the acid value to reach the target. Then, it was cooled to room temperature, and a bisphenol fluorene type epoxy acrylate represented by the following formula (V) that was colorless and transparent was obtained.
[0104] [化 8] [0104] [Chemical 8]
Figure imgf000032_0001
Figure imgf000032_0001
[0105] 次いで、このようにして得られた上記のビスフエノールフルオレン型エポキシアタリレ ート 307. Ogにプロピレングリコールモノメチルエーテルアセテート（PGMEA) 600g をカロえて溶解した。その後、ベンゾフエノンテトラカルボン酸二無水物 80. 5g及び臭 化テトラェチルアンモ -ゥム lgを混合し、徐々に昇温して 110〜 115°Cで 4時間反応 させた。酸無水物基の消失を確認した後、 1, 2, 3, 6—テトラヒドロ無水フタル酸 38. Ogを混合し、 90°Cで 6時間反応させ、上記式 (I)に相当する化合物 1を得た。酸無水 物基の消失は IRスペクトルにより確認した。 [0105] Next, 600 g of propylene glycol monomethyl ether acetate (PGMEA) was added and dissolved in the bisphenol fluorene type epoxy acrylate 307. Og thus obtained. Then, 80.5 g of benzophenone tetracarboxylic dianhydride and odor Tetraethylammonium chloride was mixed and gradually heated to react at 110 to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 1, 2, 3, 6-tetrahydrophthalic anhydride 38. Og was mixed and reacted at 90 ° C for 6 hours to obtain the compound 1 corresponding to the above formula (I). Obtained. The disappearance of the acid anhydride group was confirmed by IR spectrum.
[0106] ここでィ匕合物 1は、上記式 (I)に示すィ匕合物において、 Xは、上記式 (Π)で示される 基であり、 Yは 1, 2, 3, 6—テトラヒドロ無水フタル酸力 酸無水物基（— CO— O— C O—）を除いた残基、 Zは 3, 3', 4, 4'一べンゾフエノンテトラカルボン酸二無水物から 酸無水物を除いた残基であるとともに、 YZZモル比は 50. 0/50. 0である化合物 に相当する。 Here, compound 1 is the compound represented by the above formula (I), X is a group represented by the above formula (上 記), and Y is 1, 2, 3, 6— Tetrahydrophthalic anhydride Power residue after removal of acid anhydride group (—CO—O—CO—), Z is from 3, 3 ', 4, 4' monobenzophenone tetracarboxylic dianhydride to acid anhydride It corresponds to a compound having a YZZ molar ratio of 50.0 / 50.0.
[0107] この化合物 1をアルカリ可溶性高分子とし、 PGMEA中固形分濃度が 40質量％に なるように調整し、以下の感光性榭脂組成物溶液の作成に用いた。  [0107] This compound 1 was made into an alkali-soluble polymer, adjusted so that the solid content concentration in PGMEA was 40% by mass, and used to prepare the following photosensitive resin composition solution.
[実施例 1〜9]  [Examples 1 to 9]
<感光性榭脂組成物溶液の作製 >  <Preparation of photosensitive resin composition solution>
表 1に示す割合で感光性榭脂組成物の各成分を混合し、メチルェチルケトンを溶 媒として固形分量が 10質量％の感光性榭脂組成物溶液を得た。なお、表 1において 、略号 (A— 1〜F— 1)で表した感光性榭脂組成物を構成する成分は次に示すとおり である。  Each component of the photosensitive resin composition was mixed in the ratio shown in Table 1 to obtain a photosensitive resin composition solution having a solid content of 10% by mass using methyl ethyl ketone as a solvent. In Table 1, components constituting the photosensitive resin composition represented by abbreviations (A-1 to F-1) are as shown below.
A— 1：合成例 1で合成した化合物 1の PGMEA溶液（固形分濃度 40質量％) A—1: PGMEA solution of Compound 1 synthesized in Synthesis Example 1 (solid content: 40% by mass)
A— 2：メタクリル酸べンジル Zメタクリル酸の共重合体のメチルェチルケトン溶液（質 量比 85Z15、重量平均分子量 30000、固形分濃度 40質量％) A-2: Methyl ethyl ketone solution of benzyl methacrylate Z methacrylic acid copolymer (mass ratio 85Z15, weight average molecular weight 30000, solid content concentration 40% by mass)
A— 3：スチレン Zメタクリル酸メチル Zメタクリル酸の共重合体のメチルェチルケトン 溶液 (質量比 25Z50Z25、重量平均分子量 55000、固形分濃度 40質量％)。 Α— 4 :スチレン Zメタクリル酸メチル Zメタクリル酸の共重合体のメチルェチルケトン溶液 (質量比 25Z50Z25、重量平均分子量 20000、固形分濃度 40質量％)。 Β— 1 :ぺ ンタエリスリトールテトラアタリレート  A-3: Methyl ethyl ketone solution of copolymer of styrene Z methyl methacrylate Z methacrylic acid (mass ratio 25Z50Z25, weight average molecular weight 55000, solid content concentration 40 mass%). Α-4: Methyl ethyl ketone solution of copolymer of styrene Z methyl methacrylate Z methacrylic acid (mass ratio 25Z50Z25, weight average molecular weight 20000, solid content concentration 40 mass%). Β— 1: Pentaerythritol tetraatrate
Β— 2 :コハク酸変性ペンタエリスリトールトリアタリレート（東亜合成社製ァロニックス TO - 756)  Β—2: Succinic acid-modified pentaerythritol triatalylate (Aronix TO-756 manufactured by Toa Gosei Co., Ltd.)
C— 1 : 1— [9—ェチル—6— (2—メチルベンゾィル）—9. H. —力ルバゾール—3— ィル]—ェタン一 1—オンォキシム O アセテート （チバ'スペシャルティ ·ケミカル ズ社製 IRGACURE OXE-02) C— 1: 1— [9-Ethyl-6- (2-Methylbenzoyl) —9. H. —Strengthen rubazole—3— [Yil] —Ethan 1—Onoxime O acetate (IRGACURE OXE-02, manufactured by Ciba Specialty Chemicals)
D— 1 :カーボンブラック  D— 1: Carbon black
<感光性樹脂積層体の作製 >  <Production of photosensitive resin laminate>
前記感光性榭脂組成物を、厚さ 20 mのポリエチレンテレフタレート製支持層にバ —コ—タ—を用いて均一に塗布し、 95°Cの乾燥機中で 3分間乾燥する。次いで、感 光性榭脂層に厚さ 20 mの延伸ポリプロピレン製保護層を張り合わせ、実施例 1〜9 の感光性榭脂積層体を得た。  The photosensitive resin composition is uniformly applied to a polyethylene terephthalate support layer having a thickness of 20 m using a bar coater, and dried in a dryer at 95 ° C. for 3 minutes. Next, a 20-m thick stretched polypropylene protective layer was laminated to the photosensitive resin layer to obtain the photosensitive resin laminates of Examples 1-9.
[0108] 尚、感光性榭脂組成物の塗布後、ムラが無いかを観察し次のように支持層への塗 工性を評価した。 [0108] After application of the photosensitive resin composition, it was observed whether there was any unevenness, and the coating property to the support layer was evaluated as follows.
〇：塗布ムラがなく均一  ○: Uniform with no coating unevenness
X：塗布ムラがあり不均一  X: Uneven coating due to unevenness
<ブラックマトリックスの形成 >  <Formation of black matrix>
上記実施例 1〜9の感光性榭脂積層体の保護層を剥がして、ガラス基板にラミネー トした。 10cm角基板に感光性榭脂積層体をラミネートするのに約 5秒を要した。その 後、ライン幅：スペース幅が 1 : 9のマトリックスパターンのガラスマスクを通して、超高 圧水銀ランプ（(株)ォ―ク製作所製 HMW— 801)により 40mj/cm2で露光した。こ のとき支持層とガラスマスクとの距離を 100 mに設定した。支持層を剥離した後、 0 . 05質量％の水酸ィ匕カリウム水溶液を 23°Cでスプレーし、未露光部分の光重合性 榭脂層を溶解除去して現像した。このときのスプレー時間は、未露光部分の光重合 性榭脂層がガラス基板力もちようど除去されたときの時間 (最小現像時間）の 1. 5倍と した。その後、 240°Cで 60分ポストベータし、ブラックマトリックスを形成した。 The protective layers of the photosensitive resin laminates of Examples 1 to 9 were peeled off and laminated to a glass substrate. It took about 5 seconds to laminate the photosensitive resin laminate on a 10cm square substrate. Thereafter, the film was exposed at 40 mj / cm 2 with a super high pressure mercury lamp (HMW-801, manufactured by Oak Manufacturing Co., Ltd.) through a glass mask having a 1: 9 line width: space width. At this time, the distance between the support layer and the glass mask was set to 100 m. After peeling off the support layer, 0.05 mass% aqueous solution of potassium hydroxide and potassium hydroxide was sprayed at 23 ° C., and the photopolymerizable resin layer in the unexposed portion was dissolved and removed for development. The spraying time at this time was 1.5 times the time (minimum development time) when the photopolymerizable resin layer in the unexposed area was removed with the glass substrate force. Thereafter, post-beta was performed at 240 ° C for 60 minutes to form a black matrix.
[0109] 尚、上記ブラックマトリックスの形成工程にて、露光後に支持層を剥離した際、感光 性榭脂層がガラス基板に転写される様を観察し、次のようにガラス基板への転写性を 評価した。転写性の評価には、ライン幅:スペース幅が 1 : 9のマトリックスパターン以 外にもべタパターンを露光し、同時に評価した。 [0109] In the above black matrix formation step, when the support layer was peeled after exposure, it was observed that the photosensitive resin layer was transferred to the glass substrate, and the transferability to the glass substrate was as follows. Evaluated. For the evaluation of transferability, a solid pattern was exposed in addition to a matrix pattern having a line width: space width of 1: 9 and evaluated simultaneously.
(ガラス基板への転写性）  (Transferability to glass substrate)
〇：感光性榭脂層全体がガラス基板に転写される。 △:ベタパターンが露光された部分の一部が支持層と共に剥離するが、マトリックス パターンは問題なく転写される。 ◯: The entire photosensitive resin layer is transferred to the glass substrate. Δ: Part of the exposed portion of the solid pattern is peeled off together with the support layer, but the matrix pattern is transferred without any problem.
△△:ベタパターンが露光された部分の一部が支持層と共に剥離し、マトリックスパ ターンの一部も支持層とともに剥離する。  ΔΔ: Part of the exposed portion of the solid pattern is peeled off together with the support layer, and part of the matrix pattern is peeled off together with the support layer.
X：マトリックスパターン、ベタパターンにかかわらず、支持層とともに剥離される。 <ブラックマトリックスの評価 >  X: It peels with a support layer irrespective of a matrix pattern and a solid pattern. <Evaluation of black matrix>
(1)膜厚  (1) Film thickness
上記のガラス基板上のブラックマトリックスにつ 、て、テンコール'インスツルメンッ社 製アルファステップ (AS200)を用いてガラス基板に形成されたパターンの高さを測 定し、これを膜厚 m)とした。  For the black matrix on the glass substrate, the height of the pattern formed on the glass substrate was measured using an alpha step (AS200) manufactured by Tencor Instruments Co., Ltd., and this was defined as the film thickness m).
(2)遮光性  (2) Light shielding
上記のブラックマトリックスと同様の方法でベタパターンを作成し、ダレタグマクベス 社製光学濃度計 D200— IIを用いて光学濃度を測定した。光学濃度とは、ある光源 の光に対して入射光強度を I、透過光強度を Iとした場合に、光学濃度 =log (I /\  A solid pattern was prepared in the same manner as the above black matrix, and the optical density was measured using a Daletag Macbeth optical densitometer D200-II. The optical density is the optical density = log (I / \), where I is the incident light intensity and I is the transmitted light intensity.
0 10 0 0 10 0
)の関係で表される。光学濃度を上記膜厚で除した値をもとめ、これを遮光性とした。 遮光性の評価は以下のランクに従った。 ). A value obtained by dividing the optical density by the above film thickness was obtained, and this was regarded as a light shielding property. The light shielding property was evaluated according to the following rank.
〇：3以上  ○: 3 or more
△ : 2以上 3未満  △: 2 or more and less than 3
X： 2未満  X: Less than 2
(3)感度  (3) Sensitivity
ガラス基板に感光性榭脂積層体をラミネートし、スト一ファー 21段ステップタブレット (タブレットの段数が 1段につき光学濃度 0. 15変化するマスクフィルム）を通して、上 記と同じように露光'現像、ポストベータしたガラス基板を、ステップタブレットパターン が何段まで残っているかを目視で読み取った。感度の評価は以下のランクに従った  Laminate a photosensitive resin laminate on a glass substrate, and then expose and develop it in the same way as above, through a stiffer 21-step tablet (a mask film in which the number of tablet steps changes by 0.15 in optical density). The post-beta glass substrate was visually read to see how many step tablet patterns remained. Sensitivity was evaluated according to the following rank
〇：3段以上 ○: 3 steps or more
△ : 2段以上 3段未満  △: 2 steps or more and less than 3 steps
X : 2段未満 (4)密着性 X: Less than 2 steps (4) Adhesion
ライン幅：スペース幅 = 1： 9のマトリックスパターンマスクを通して 40mjZcm2で露 光し、最小現像時間の 1. 5倍の時間現像してマトリックスパターンを形成した。マトリ ックスパターンが形成できているかどうかを光学顕微鏡で目視にて観察し、形成可能 であった最小のマトリックスパターンに対応するマスク幅（ μ m)を密着性とした。密着 性の評価は以下のランクに従った。 The matrix pattern was formed by exposing at 40 mjZcm 2 through a matrix pattern mask of line width: space width = 1: 9 and developing for 1.5 times the minimum development time. Whether a matrix pattern was formed was visually observed with an optical microscope, and the mask width (μm) corresponding to the smallest matrix pattern that could be formed was defined as adhesion. The evaluation of adhesion was according to the following rank.
μ m未满  μm
Α : 5 μ m以上 10 μ m未満  Α: 5 μm or more and less than 10 μm
X : 10 /ζ πι以上  X: 10 / ζ πι or more
(5)過現像時の線幅安定性  (5) Line width stability during over-development
実施例 2および比較例 2で用いた感光性榭脂積層体をガラス基板にラミネートし、 4 OmjZcm2で露光し、現像時間を最小現像時間で除した値が 1. 1 (最小現像時間付 近相当）および 1. 6 (過現像時相当）となるように現像し、ブラックマトリックスを形成し た。マスク線幅 20 mに対応するブラックマトリックスの線幅を測長顕微鏡により測定 した。実施例 10および 11ならびに比較例 8および 9として結果を表 2にまとめた。実 施例 2の感光性榭脂積層体は比較例 2の感光性榭脂積層体に比べて線幅の変化が 小さい事が分かる。 The photosensitive榭脂laminate used in Example 2 and Comparative Example 2 was laminated on a glass substrate, exposed with 4 OmjZcm 2, a value obtained by dividing the developing time at the minimum developing time is 1. close with 1 (minimum developing time Equivalent) and 1.6 (equivalent to over-development) to form a black matrix. The line width of the black matrix corresponding to the mask line width of 20 m was measured with a length measuring microscope. The results are summarized in Table 2 as Examples 10 and 11 and Comparative Examples 8 and 9. It can be seen that the change in line width of the photosensitive resin laminate of Example 2 is smaller than that of the photosensitive resin laminate of Comparative Example 2.
[実施例 12〜13] [Examples 12 to 13]
<カラー画素の作成 > <Create color pixels>
上記実施例 1において、 D—1 :カーボンブラックの代わりに、 D - 2 : C. I.ビグメント レッド 254および D— 3 :ビグメントイエロー 139を用いて、実施例 1と同様に混合し、 感光性榭脂組成物溶液 14および 15を作製する。  In Example 1 above, D-1: CI Pigment Red 254 and D-3: Pigment Yellow 139 were used in the same manner as in Example 1 instead of carbon black. Make composition solutions 14 and 15.
前記感光性榭脂組成物溶液 14および 15を、厚さ 20 mのポリエチレンテレフタレー ト製ベースフィルムにバ—コ—タ—を用 、て均一に塗布し、 95°Cの乾燥機中で 3分 間乾燥する。次いで、得られる光重合性榭脂組成物積層体上に厚さ 25 mのポリエ チレン製保護フィルムを張り合わせ、実施例 12および 13の感光性榭脂積層体を得 ることができる。実施例 12および 13の感光性榭脂積層体の保護フィルムを剥がして 、ガラス基板にラミネートした後、ライン幅 Zスペース幅が 5 μ m/25 μ mのパターン のマスクフィルムを通して、超高圧水銀ランプ（(株)オーク製作所製 HMW— 801)に より 40mjZcm2で露光する。支持フィルムを剥離した後、 0. 05質量％の水酸ィ匕カリ ゥム水溶液を 23°Cで約 30秒間スプレ―し、未露光部分の感光性榭脂層を溶解除去 して現像する。その後、 200°Cで 15分ポストベータし、カラー画素を形成する。 The photosensitive resin composition solutions 14 and 15 were uniformly applied to a polyethylene terephthalate base film having a thickness of 20 m using a bar coater, and the coating was performed in a dryer at 95 ° C. Dry for minutes. Next, a 25 m thick polyethylene protective film is laminated on the resulting photopolymerizable resin composition laminate, and the photosensitive resin laminates of Examples 12 and 13 can be obtained. After peeling off the protective film of the photosensitive resin laminate of Examples 12 and 13 and laminating it on a glass substrate, a pattern with a line width Z space width of 5 μm / 25 μm The film is exposed to 40 mjZcm 2 with an ultra-high pressure mercury lamp (HMW-801 manufactured by Oak Manufacturing Co., Ltd.). After the support film is peeled off, 0.05% by weight aqueous solution of hydroxyaluminum hydroxide is sprayed at 23 ° C for about 30 seconds to dissolve and remove the unexposed photosensitive resin layer. After that, post-beta at 200 ° C for 15 minutes to form color pixels.
[実施例 14〜 17および比較例 10]  [Examples 14 to 17 and Comparative Example 10]
表 1の実施例 14〜 17および比較例 10に示す割合で感光性榭脂組成物の各成分 を混合し、メチルェチルケトンを溶媒として固形分量が 10質量％の感光性榭脂組成 物溶液 14〜 17および比較感光性榭脂組成物溶液 10を得た。感光性榭脂組成物溶 液 14〜 17および比較感光性榭脂組成物溶液 10を、厚さ 20 mのポリエチレンテレ フタレート製支持層にバ—コ―タ—を用いて均一に塗布し、 95°Cの乾燥機中で 3分 間乾燥する。次いで、感光性榭脂層に厚さ 20 mの延伸ポリプロピレン製保護層を 張り合わせ、実施例 14〜17および比較例 10の感光性榭脂積層体を得た。  The components of the photosensitive resin composition were mixed in the ratios shown in Examples 14 to 17 and Comparative Example 10 in Table 1, and the photosensitive resin composition solution having a solid content of 10% by mass using methyl ethyl ketone as a solvent. 14-17 and the comparative photosensitive resin composition solution 10 were obtained. The photosensitive resin composition solutions 14 to 17 and the comparative photosensitive resin composition solution 10 were uniformly applied to a polyethylene terephthalate support layer having a thickness of 20 m using a bar coater. Dry in a ° C dryer for 3 minutes. Then, a 20 m thick stretched polypropylene protective layer was laminated to the photosensitive resin layer, and the photosensitive resin laminates of Examples 14 to 17 and Comparative Example 10 were obtained.
[0110] 上記実施例 14〜17および比較例 10の感光性榭脂積層体の保護層を剥がして、 ガラス基板にラミネートした。その後、支持層を剥離し、ライン幅:スペース幅が 1 : 9の マトリックスパターンのガラスマスクを通して、超高圧水銀ランプ（(株)ォ―ク製作所 製 HMW— 801)により lOOmjZcm2で露光した。このとき感光性榭脂層とガラスマス クとの距離を 100 /z mに設定した。次いで、 0. 05質量％の水酸ィ匕カリウム水溶液を 2 3°Cでスプレーし、未露光部分の光重合性榭脂層を溶解除去して現像した。このとき のスプレー時間は、未露光部分の光重合性榭脂層がガラス基板力 ちょうど除去さ れたときの時間（最小現像時間）の 1. 5倍とした。その後、 240°Cで 60分ポストベータ し、ブラックマトリックスを形成した。結果を表 3に示す。 [0110] The protective layer of the photosensitive resin laminate of Examples 14 to 17 and Comparative Example 10 was peeled off and laminated to a glass substrate. Thereafter, the support layer was peeled off, and exposed to lOOmjZcm 2 with a super high pressure mercury lamp (HMW-801, manufactured by Oak Manufacturing Co., Ltd.) through a glass mask having a matrix pattern with a line width: space width of 1: 9. At this time, the distance between the photosensitive resin layer and the glass mask was set to 100 / zm. Subsequently, 0.05% by mass of a potassium hydroxide aqueous solution of sodium hydroxide was sprayed at 23 ° C., and the photopolymerizable resin layer in the unexposed part was dissolved and removed for development. The spraying time at this time was 1.5 times the time (minimum development time) when the photopolymerizable resin layer in the unexposed area was just removed. Thereafter, it was post-betaned at 240 ° C for 60 minutes to form a black matrix. The results are shown in Table 3.
[0111] 尚、ガラス基板への転写性は、ノターンを露光する前に支持層を剥離するので、次 の様に評価した。  [0111] Transferability to a glass substrate was evaluated as follows because the support layer was peeled off before exposure of noturn.
〇：感光性榭脂層全体がガラス基板に転写される。  ◯: The entire photosensitive resin layer is transferred to the glass substrate.
X：感光性榭脂層の一部が支持層とともに剥離される。  X: A part of the photosensitive resin layer is peeled off together with the support layer.
[比較例 1〜7]  [Comparative Examples 1-7]
表 1に示す割合で比較例 1〜7の感光性榭脂組成物の各成分を混合し、固形分量 が 10重量％の比較感光性榭脂組成物溶液 1〜7を得た。この比較感光性榭脂組成 物溶液 1〜7を、実施例と同じようにして厚さ 20 mのポリエチレンテレフタレート製 ベースフィルム上に塗布し、厚さ 20 mの延伸ポリプロピレン製保護層を張り合わせ て、比較例 1〜7の感光性榭脂積層体を作製した。これらの比較例 1〜7の感光性榭 脂積層体を用いて、実施例と同じようにして、ガラス基板上にブラックマトリックスを形 成した。評価についても、実施例と同じ項目を評価し、結果を表 1に示した。 The components of the photosensitive resin compositions of Comparative Examples 1 to 7 were mixed at the ratio shown in Table 1 to obtain Comparative photosensitive resin compositions solutions 1 to 7 having a solid content of 10% by weight. This comparative photosensitive resin composition In the same manner as in the Examples, the product solutions 1 to 7 were applied onto a 20 m thick polyethylene terephthalate base film, and a 20 m thick stretched polypropylene protective layer was laminated to the photosensitive films of Comparative Examples 1 to 7. A hydrophilic resin laminate was produced. Using these photosensitive resin laminates of Comparative Examples 1 to 7, a black matrix was formed on a glass substrate in the same manner as in the Examples. Regarding the evaluation, the same items as in the examples were evaluated, and the results are shown in Table 1.
尚、比較例 4の感光性榭脂組成物は、ベースフィルムに塗布乾燥後、塗布ムラが見 られた。また、未露光部分の感光性榭脂層と支持層との粘着性が高ぐ露光部分は 支持層を剥離する時に共に基板カゝら剥離された。比較例 5の感光性榭脂組成物は、 塗布後、 目視で明らかなほど光学濃度の薄い部分が生じ均一に塗布することができ なかった。  The photosensitive resin composition of Comparative Example 4 showed coating unevenness after coating and drying on the base film. Further, the exposed portion where the adhesiveness between the photosensitive resin layer and the support layer in the unexposed portion was high was peeled off from the substrate cover when the support layer was peeled off. The photosensitive resin composition of Comparative Example 5 had a portion with a low optical density as apparent to the eye after application, and could not be applied uniformly.
[0112] [比較例 11]  [0112] [Comparative Example 11]
実施例 3で作成した感光性榭脂組成物溶液 3を、スピンコーター（ミカサスピンコータ 一 1H— 360S)を用い、 10cm角のガラス基板に、毎分 500回転でスピンコートした。 塗布後、基板中心部力ゝら辺縁部に向カゝつて放射状の塗布ムラが生じた。また基板を 縁取るように辺縁部にも約 lmm程度の塗布ムラが生じた。ガラス基板に感光性榭脂 層を積層するにはさらにこれをオーブン中 80°Cで 10分乾燥する必要があった。 さらに、実施例 3で実施したのと同様に、露光現像してブラックマトリックスの形成を試 みたところ、現像後基板上にパターンは残らな力 た。  The photosensitive resin composition solution 3 prepared in Example 3 was spin-coated on a 10 cm square glass substrate at 500 rpm using a spin coater (Mikasa Spin Coater 1H-360S). After coating, radial coating unevenness occurred toward the edge of the substrate center. In addition, coating irregularities of about lmm occurred at the edge as well as the substrate. In order to laminate the photosensitive resin layer on the glass substrate, it was necessary to further dry it in an oven at 80 ° C for 10 minutes. Furthermore, as in the case of Example 3, exposure and development were performed to form a black matrix. As a result, a pattern remained on the substrate after development.
[0113] [表 1] [0113] [Table 1]
Figure imgf000039_0001
Figure imgf000039_0001
[0114] [表 2][0114] [Table 2]
Figure imgf000040_0001
Figure imgf000040_0001
[0115] [表 3] [0115] [Table 3]
Figure imgf000040_0002
Figure imgf000040_0002
産業上の利用可能性 本発明は、液晶ディスプレイ、有機 ELディスプレイ、プラズマディスプレイなどのフ ラットパネルディスプレイや、上記液晶ディスプレイや有機 ELディスプレイに用いられ るカラーフィルタの分野で利用でき、特に液晶ディスプレイの分野で好適に用いられ る。 Industrial applicability The present invention can be used in the field of flat panel displays such as liquid crystal displays, organic EL displays, and plasma displays, and color filters used in the above liquid crystal displays and organic EL displays, and is particularly preferably used in the field of liquid crystal displays. The

Claims

請求の範囲 The scope of the claims
少なくとも支持層と感光性榭脂層とを積層してなり、該感光性榭脂層が、 At least a support layer and a photosensitive resin layer are laminated, and the photosensitive resin layer is
下記式 (I)で表されるアルカリ可溶性高分子 3〜40質量％、 3 to 40% by mass of an alkali-soluble polymer represented by the following formula (I),
重量平均分子量が 3, 000〜100, 000であるメタクリル酸べンジル又はアクリル酸べ ンジルを共重合したアルカリ可溶性高分子及び重量平均分子量が 3, 000-50, 00 0であるアクリル系のアルカリ可溶性高分子力もなる群より選ばれる少なくとも一種の アルカリ可溶性高分子 1〜40質量％、 Alkali-soluble polymer copolymerized with benzyl methacrylate or benzyl acrylate with a weight average molecular weight of 3,000 to 100,000 and acrylic alkali-soluble with a weight average molecular weight of 3,000-50,000 1 to 40% by mass of at least one alkali-soluble polymer selected from the group consisting of polymer strength,
エチレン性不飽和二重結合を有する光重合性化合物 3〜25質量％、 3-25% by mass of a photopolymerizable compound having an ethylenically unsaturated double bond,
光重合開始剤 0. 1〜20質量％、 Photopolymerization initiator 0.1 to 20% by mass,
着色顔料 40〜70質量％を含み、かつ、 Containing 40 to 70% by weight of a color pigment, and
該式 (I)で表されるアルカリ可溶性高分子:該重量平均分子量が 3, 000〜： L00, 00 0であるメタクリル酸べンジル又はアクリル酸ベンジルを共重合したアルカリ可溶性高 分子及び重量平均分子量が 3, 000〜50, 000であるアクリル系のアルカリ可溶性 高分子力 なる群より選ばれる少なくとも一種のアルカリ可溶性高分子 (質量比） = 1 : 5〜16：丄 Alkali-soluble polymer represented by formula (I): Alkali-soluble polymer and weight-average molecular weight copolymerized with benzyl methacrylate or benzyl acrylate having a weight-average molecular weight of 3,000-: L00,000 Acrylic alkali-soluble polymer having a molecular weight of 3,000 to 50,000 at least one alkali-soluble polymer (mass ratio) selected from the group consisting of 1: 5 to 16: 丄
である感光性榭脂組成物からなる感光性榭脂積層体。 A photosensitive resin laminate comprising a photosensitive resin composition.
[化 1] [Chemical 1]
COOHCOOH
HOOC-Y— CO— 0- -X-O-CO—； CO-O- _χ— O— CO— Y— COOH ( I ) HOOC-Y— CO— 0- -X-O-CO—; CO-O- _χ— O— CO— Y— COOH (I)
COOH  COOH
n  n
(式 (I)中、 Xは下記式 (Π)で表される基、 Υはジカルボン酸無水物の酸無水物基を 除いた残基、 Ζはテトラカルボン酸二無水物の酸無水物基を除いた残基、 ηは 1〜20 の整数である。下記式 (Π)中の Rおよび Rはそれぞれ互いに独立な Ηまたは CH (In the formula (I), X is a group represented by the following formula (Π), Υ is a residue excluding an acid anhydride group of a dicarboxylic anhydride, Ζ is an acid anhydride group of a tetracarboxylic dianhydride, Η is an integer of 1 to 20. R and R in the following formula (Π) are each independently Η or CH
1 2 3 基を表す。 )  1 2 3 represents a group. )
[化 2] [Chemical 2]
Figure imgf000043_0001
Figure imgf000043_0001
[2] 該感光性樹脂層が、  [2] The photosensitive resin layer is
上記式 (I)で表されるアルカリ可溶性高分子 3〜40質量％、  3-40% by mass of the alkali-soluble polymer represented by the above formula (I),
重量平均分子量が 3, 000〜100, 000であるメタクリル酸べンジル又はアクリル酸べ ンジルを共重合したアル力リ可溶性高分子 1〜40質量％、  1 to 40% by mass of an alcoholic soluble polymer copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000,
エチレン性不飽和二重結合を有する光重合性化合物 3〜25質量％、  3-25% by mass of a photopolymerizable compound having an ethylenically unsaturated double bond,
光重合開始剤 0. 1〜20質量％、  Photopolymerization initiator 0.1 to 20% by mass,
着色顔料 40〜70質量％を含み、かつ、  Containing 40 to 70% by weight of a color pigment, and
該式 (I)で表されるアルカリ可溶性高分子:該重量平均分子量が 3, 000〜： L00, 00 0であるメタクリル酸べンジル又はアクリル酸ベンジルを共重合したアルカリ可溶性高 分子 (質量比） = 1 : 5〜16 : 1  Alkali-soluble polymer represented by formula (I): Alkali-soluble polymer (mass ratio) obtained by copolymerization of benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to L0,000 = 1: 5 to 16: 1
である感光性榭脂組成物カゝらなる請求項 1記載の感光性榭脂積層体。  2. The photosensitive resin laminate according to claim 1, wherein the photosensitive resin composition is:
[3] 該感光性樹脂層が、 [3] The photosensitive resin layer is
上記式 (I)で表されるアルカリ可溶性高分子 3〜40質量％、  3-40% by mass of the alkali-soluble polymer represented by the above formula (I),
重量平均分子量が 3, 000〜50, 000であるメタクリル酸べンジル又はアクリル酸べ ンジルを共重合したアルカリ可溶性高分子 5〜40質量％、  5-40% by mass of an alkali-soluble polymer copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 50,000,
エチレン性不飽和二重結合を有する光重合性化合物 5〜25質量％、  5-25% by mass of a photopolymerizable compound having an ethylenically unsaturated double bond,
光重合開始剤 0. 1〜20質量％、  Photopolymerization initiator 0.1 to 20% by mass,
着色顔料 40〜70質量％を含み、かつ、  Containing 40 to 70% by weight of a color pigment, and
該式 (I)で表されるアルカリ可溶性高分子:該重量平均分子量が 3, 000〜50, 000 であるメタクリル酸べンジル又はアクリル酸ベンジルを共重合したアルカリ可溶性高 分子 (質量比） = 1： 5〜5： 1である請求項 2記載の感光性榭脂積層体。  Alkali-soluble polymer represented by the formula (I): alkali-soluble polymer (mass ratio) = 1 copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 50,000 The photosensitive resin laminate according to claim 2, which is 5 to 5: 1.
[4] 該式 (I)で表されるアルカリ可溶性高分子:該重量平均分子量が 3, 000〜： L00, 00 0であるメタクリル酸べンジル又はアクリル酸ベンジルを共重合したアルカリ可溶性高 分子及び重量平均分子量が 3, 000〜50, 000であるアクリル系のアルカリ可溶性 高分子力 なる群より選ばれる少なくとも一種のアルカリ可溶性高分子 (質量比） = 2 ： 1〜16： 1である請求項 1記載の感光性榭脂積層体。 [4] The alkali-soluble polymer represented by the formula (I): the alkali-soluble polymer obtained by copolymerization of benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to L0,000 Acrylic alkali-soluble polymer having a molecular weight and a weight average molecular weight of 3,000 to 50,000 At least one alkali-soluble polymer (mass ratio) selected from the group consisting of: 2: 1 to 16: 1 Item 2. A photosensitive resin laminate according to Item 1.
[5] 感光性榭脂組成物中に、光重合開始剤としてォキシムエステルイ匕合物を含む請求 項 1〜4のいずれか一項に記載の感光性榭脂積層体。  [5] The photosensitive resin laminate according to any one of [1] to [4], wherein the photosensitive resin composition contains an oxime ester compound as a photopolymerization initiator.
[6] 感光性榭脂組成物中に、エチレン性不飽和二重結合を有する光重合性ィ匕合物とし て下記式 (ΠΙ)で表される化合物を含む請求項 1〜4の 、ずれか一項に記載の感光 性樹脂積層体。  [6] The deviation of claims 1-4, wherein the photosensitive resin composition contains a compound represented by the following formula (ΠΙ) as a photopolymerizable compound having an ethylenically unsaturated double bond: The photosensitive resin laminated body as described in any one of the above.
[化 3]  [Chemical 3]
Figure imgf000044_0001
Figure imgf000044_0001
(式 (ΠΙ)中、 R、 Rおよび Rは、それぞれ互いに独立な Hまたは CH基を表す。 R (In the formula (ΠΙ), R, R and R each independently represent a H or CH group. R
3 4 5 3 6 は 2価の連結基で、炭素数 2〜8のアルキレン基、炭素数 3〜 10のシクロアルキレン 基、及び炭素数 6〜10のフエ-レン基力もなる群より選ばれる一種の基を表す。 ) 着色顔料が黒色顔料である請求項 1に記載の感光性榭脂積層体。  3 4 5 3 6 is a divalent linking group selected from the group consisting of an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, and a phenyl group having 6 to 10 carbon atoms. Represents a group of 2. The photosensitive resin laminate according to claim 1, wherein the colored pigment is a black pigment.
請求項 1〜4のいずれか一項に記載の感光性榭脂積層体を、少なくとも、基板にラミ ネートする工程、露光する工程、現像する工程を順に含むカラー画素付き基板の製 造方法。  A method for producing a substrate with a color pixel, comprising at least a step of laminating the photosensitive resin laminate according to any one of claims 1 to 4 on a substrate, an exposure step, and a development step.
[9] 請求項 7に記載の感光性榭脂積層体を、少なくとも、基板にラミネートする工程、露 光する工程、支持層を剥離する工程、現像する工程を順に含むブラックマトリックス 付き基板の製造方法。  [9] A method for producing a substrate with a black matrix, comprising at least the step of laminating the photosensitive resin laminate according to claim 7 on a substrate, the step of exposing, the step of peeling off the support layer, and the step of developing. .
[10] 請求項 7に記載の感光性榭脂積層体を、少なくとも、基板にラミネートする工程、支 持層を剥離する工程、露光する工程、現像する工程を順に含むブラックマトリックス 付き基板の製造方法。 [11] 少なくとも、請求項 9又は 10に記載の方法で基板上にブラックマトリックスを形成する 工程、該ガラス基板上のブラックマトリックスで覆われて 、な 、部分の少なくとも一部 に感熱性または感光性のカラーインクをインクジェット方式により印刷する印刷工程を 順に含むカラーフィルタの製造方法。 [10] A method for producing a substrate with a black matrix, comprising at least a step of laminating the photosensitive resin laminate according to claim 7 on a substrate, a step of peeling off the support layer, a step of exposing, and a step of developing. . [11] At least a step of forming a black matrix on the substrate by the method according to claim 9 or 10, wherein at least a part of the portion is covered with a black matrix on the glass substrate, and heat sensitive or photosensitive. A method for producing a color filter, which sequentially comprises a printing step of printing the color ink by an inkjet method.
[12] 請求項 11記載の方法により製造されるカラーフィルタ。  [12] A color filter produced by the method according to claim 11.
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JP4954194B2 (en) 2012-06-13
KR101014163B1 (en) 2011-02-14
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CN101401036B (en) 2011-12-07
KR20080096700A (en) 2008-10-31

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