CN113867099A - Photosensitive resin composition for black resist, method for producing same, light-shielding film, color filter, touch panel, and display device - Google Patents

Photosensitive resin composition for black resist, method for producing same, light-shielding film, color filter, touch panel, and display device Download PDF

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Publication number
CN113867099A
CN113867099A CN202110731043.7A CN202110731043A CN113867099A CN 113867099 A CN113867099 A CN 113867099A CN 202110731043 A CN202110731043 A CN 202110731043A CN 113867099 A CN113867099 A CN 113867099A
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Prior art keywords
light
photosensitive resin
dispersant
resin composition
acid
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Chinese (zh)
Inventor
内田一幸
新名将司
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel and Sumikin Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G02—OPTICS
    • 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
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Abstract

The invention relates to a photosensitive resin composition for a black resist, a manufacturing method thereof, a shading film, a color filter, a touch screen and a display device. The photosensitive resin composition for a black resist of the present invention comprises: (A) a photosensitive resin containing an unsaturated group, (B) a photopolymerizable monomer having at least two unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-shielding component selected from the group consisting of black pigments, mixed color pigments and light-shielding materials, (E) silica particlesAnd (F) a dispersant. The dispersant (F) has an acid value and an amine value, both of which are 10mgKOH/g or more and 80mgKOH/g or less, and the total mass (m) of the dispersant (F)F) Relative to the total mass (m) of the (E) silica particlesE) Ratio (m)F/mE) 0.02 to 0.60.

Description

Photosensitive resin composition for black resist, method for producing same, light-shielding film, color filter, touch panel, and display device
Technical Field
The present invention relates to a photosensitive resin composition for a black resist, a method for producing the photosensitive resin composition, a light-shielding film obtained by curing the photosensitive resin composition for a black resist, a color filter and a touch panel each having the light-shielding film, and a display device having the color filter and the touch panel.
Background
In recent years, with the development of mobile terminals, display devices such as touch panels and liquid crystal panels used for outdoor or in-vehicle applications have increased. In the display device, a light shielding film is provided on a touch panel outer frame to shield light leakage in a peripheral portion of a liquid crystal panel on a back surface, and a black matrix is provided on the liquid crystal panel to suppress light leakage from a screen at the time of black display and to suppress color mixing between adjacent color resists.
In a display device or the like, in order to suppress light leakage or the like and improve visibility of a screen of the display device or the like, the light-shielding property of a light-shielding film (light transmittance of the light-shielding film) may be improved by increasing the concentration of a black pigment in the light-shielding film. Since the refractive index of the black pigment is higher than that of the transparent substrate or the curable resin, if the concentration of the black pigment in the light-shielding film is increased, the reflectance is increased when viewed from the surface of the transparent substrate opposite to the surface on which the light-shielding film is formed. Therefore, reflection at the interface between the light-shielding film formed on the transparent substrate and the transparent substrate increases, and a problem occurs in which the black matrix boundary is conspicuous due to reflection on the light-shielding film or a difference in reflectance with the colored portion of the color filter.
Therefore, a photosensitive resin composition for a black resist having both high light-shielding properties and low reflectance, and a light-shielding film and a color filter obtained by curing the same are desired.
For example, patent document 1 discloses a black photosensitive resin composition comprising: hydrophobic silica particles and a specific dispersant (urethane dispersant). By using the hydrophobic silica particles and a specific dispersant, a black matrix having both high light-shielding properties and low reflectance can be formed.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent laid-open No. 2015-161815 publication
Disclosure of Invention
[ problems to be solved by the invention ]
However, as a result of studies by the present inventors, the black photosensitive resin composition described in patent document 1 has the following problems: in the pattern formation, the pattern edge portion is jagged, or an agglomerated foreign substance derived from silica particles is generated on the black matrix.
The present invention has been made in view of the above-described circumstances, and an object thereof is to provide a photosensitive resin composition for a black resist, which has high light-shielding properties and low reflectance, can form a high-definition pattern, and can suppress the occurrence of condensed foreign matter, a light-shielding film obtained by curing the photosensitive resin composition, a color filter and a touch panel each having the light-shielding film, and a display device each having the color filter and the touch panel.
[ means for solving problems ]
The photosensitive resin composition for a black resist of the present invention comprises: (A) a photosensitive resin containing an unsaturated group, (B) a photopolymerizable monomer having at least two unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-shielding component selected from the group consisting of a black pigment, a mixed color pigment and a light-shielding material, (E) silica particles, and (F) a dispersant, wherein the dispersant has an acid value and an amine value, both of the acid value and the amine value are 10mgKOH/g or more and 80mgKOH/g or less, and the total mass (m) of the dispersant (F) isF) Relative to the total mass (m) of the (E) silica particlesE) Ratio (m)F/mE) 0.02 to 0.60.
The method for producing a photosensitive resin composition for a black resist of the present invention comprises mixing (A) a photosensitive resin containing an unsaturated group, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a light-shielding component dispersion in which a light-shielding component is dispersed in a solvent, and (E) a silica particle dispersion in which silica particles are dispersed in a solvent, wherein in the method for producing a photosensitive resin composition for a black resist, the two (E) compoundsThe silica particle dispersion contains (F) a dispersant having an acid value and an amine value, both of which are 10mgKOH/g or more and 80mgKOH/g or less, and the total mass (m) of the dispersantF) Relative to the total mass (m) of the (E) silica particlesE) Ratio (m)F/mE) 0.02 to 0.60.
The light-shielding film of the present invention is obtained by curing the photosensitive resin composition for a black resist.
The color filter of the invention is provided with the shading film as a black matrix.
The touch screen of the invention is provided with the shading film as a black matrix.
The display device of the invention is provided with the color filter or the touch screen.
[ Effect of the invention ]
According to the present invention, a photosensitive resin composition for a black resist, which has high light-shielding properties and low reflectance, can form a high-definition pattern, and can suppress the occurrence of condensed foreign matter, a light-shielding film obtained by curing the photosensitive resin composition, a color filter and a touch panel each having the light-shielding film, and a display device each having the color filter and the touch panel can be provided.
Detailed Description
The present invention will be described in detail below. The photosensitive resin composition for a black resist (hereinafter, simply referred to as "photosensitive resin composition") of the present invention comprises (a) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer having at least two or more unsaturated bonds, (C) a photopolymerization initiator, (D) at least one light-shielding component selected from a black pigment, a mixed color pigment and a light-shielding material, (E) silica particles, and (F) a dispersant. Hereinafter, the components (A) to (F) will be described.
The component (A)
The unsaturated group-containing photosensitive resin as the component (a) in the present embodiment preferably has a polymerizable unsaturated group and an acidic group for alkali solubility development in one molecule, and more preferably contains both a polymerizable unsaturated group and a carboxyl group. The resin is not particularly limited and can be widely used.
Examples of the unsaturated group-containing photosensitive resin include epoxy (meth) acrylate acid adducts obtained by: the method for producing a hydroxyl group-containing compound includes the steps of reacting (meth) acrylic acid with an epoxy compound having two glycidyl ether groups derived from a bisphenol (hereinafter, also referred to as a bisphenol-type epoxy compound represented by the general formula (1)) to obtain a compound having a hydroxyl group, and reacting a polycarboxylic acid or an anhydride thereof with the obtained compound having a hydroxyl group. The epoxy compound derived from a bisphenol means an epoxy compound obtained by reacting a bisphenol with an epihalohydrin, or an equivalent thereof. The term "(meth) acrylic acid" is a generic term for acrylic acid and methacrylic acid, and means one or both of these.
The photosensitive resin containing an unsaturated group as the component (a) is preferably a bisphenol epoxy compound represented by the following general formula (1).
[ solution 1]
Figure BDA0003138481910000041
(in the formula (1), R1、R2、R3And R4Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and X represents-CO-, -SO2-、-C(CF3)2-、-Si(CH3)2-、-CH2-、-C(CH3)2-, -O-, a fluorene-9, 9-diyl group represented by the general formula (2) or a single bond, l is an integer of 0 to 10)
[ solution 2]
Figure BDA0003138481910000042
The bisphenol-type epoxy compound represented by the general formula (1) is an epoxy compound having two glycidyl ether groups obtained by reacting a bisphenol with epichlorohydrin. The reaction is usually accompanied by oligomerization of the diglycidyl ether compound, and therefore includes an epoxy compound having two or more bisphenol skeletons.
Examples of bisphenols used in the reaction include: bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3, 5-dimethylphenyl) ketone, bis (4-hydroxy-3, 5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3, 5-dimethylphenyl) sulfone, bis (4-hydroxy-3, 5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3, 5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3, 5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dichlorophenyl) dimethylsilane, Bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dichlorophenyl) methane, bis (4-hydroxy-3, 5-dibromophenyl) methane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3, 5-dimethylphenyl) ether, bis (4-hydroxy-3, 5-dichlorophenyl) ether, 9, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9-bis (4-hydroxy-3-bromophenyl) fluorene, 9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene, 9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene, 4' -biphenol, 3, 3' -biphenol and the like. Among them, bisphenols having a fluorene-9, 9-diyl group are preferable.
Examples of the acid monoanhydride of (a) a dicarboxylic acid or tricarboxylic acid which reacts with a hydroxyl group in an epoxy (meth) acrylate molecule obtained by reacting such an epoxy compound with (meth) acrylic acid include: chain hydrocarbon dicarboxylic acid or tricarboxylic acid monoanhydrides, alicyclic dicarboxylic acid or tricarboxylic acid monoanhydrides, aromatic dicarboxylic acid or tricarboxylic acid monoanhydrides, and the like. Here, examples of the acid monoanhydrides of the chain hydrocarbon dicarboxylic or tricarboxylic acids include: succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like. Further, the acid monoanhydrides of dicarboxylic acids or tricarboxylic acids to which an arbitrary substituent is introduced are also included. In addition, examples of the acid monoanhydride of the alicyclic dicarboxylic acid or tricarboxylic acid include: acid monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and the like. Further, the acid monoanhydrides of dicarboxylic acids or tricarboxylic acids to which an arbitrary substituent is introduced are also included. In addition, examples of the acid monoanhydride of the aromatic dicarboxylic acid or tricarboxylic acid include: phthalic acid, isophthalic acid, trimellitic acid, and the like. Further, it contains an acid monoanhydride of a dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent is introduced.
As the acid dianhydride of the tetracarboxylic acid (b) to be reacted with the epoxy (meth) acrylate, an acid dianhydride of a chain hydrocarbon tetracarboxylic acid, an acid dianhydride of an alicyclic tetracarboxylic acid, or an acid dianhydride of an aromatic tetracarboxylic acid can be used. Here, examples of the acid dianhydride of the chain hydrocarbon tetracarboxylic acid include: acid dianhydrides such as butanetetracarboxylic acid, pentanetetracarboxylic acid and hexanetetracarboxylic acid. And acid dianhydrides containing tetracarboxylic acids having an arbitrary substituent introduced therein. In addition, examples of the acid dianhydride of the alicyclic tetracarboxylic acid include: acid dianhydrides such as cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid and norbornane tetracarboxylic acid. And acid dianhydrides containing tetracarboxylic acids having an arbitrary substituent introduced therein. In addition, examples of the acid dianhydride of an aromatic tetracarboxylic acid include: pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and the like. And acid dianhydrides containing tetracarboxylic acids having an arbitrary substituent introduced therein.
The molar ratio (a)/(b) of the acid monoanhydride of the (a) dicarboxylic acid or tricarboxylic acid and the acid dianhydride of the (b) tetracarboxylic acid reacted with the epoxy (meth) acrylate is preferably 0.01 to 10.0, more preferably 0.02 or more and less than 3.0. If the molar ratio (a)/(b) is out of the above range, an optimum molecular weight for producing a photosensitive resin composition having good photopatternability cannot be obtained, which is not preferable. Further, there is a downward orientation: the smaller the molar ratio (a)/(b), the larger the molecular weight and the lower the alkali solubility.
The reaction between the epoxy compound and (meth) acrylic acid and the reaction between the epoxy (meth) acrylate obtained by the reaction and the polycarboxylic acid or anhydride thereof are not particularly limited, and a known method can be used. The unsaturated group-containing photosensitive resin synthesized by the reaction preferably has a weight average molecular weight (Mw) of 2000 to 10000 and an acid value of 30 to 200 mgKOH/g. The acid value can be determined by dissolving a resin solution in dioxane, and titrating the solution with 1/10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hei Marsh industries, Ltd.). The weight average molecular weight (Mw) of the unsaturated group-containing photosensitive resin can be measured, for example, by Gel Permeation Chromatography (GPC) "HLC-8220 GPC" (manufactured by Tosoh corporation).
As for the photosensitive resin containing an unsaturated group as the component (a), other preferable examples of the resin include: a resin having a (meth) acryloyl group and a carboxyl group, which is a copolymer of (meth) acrylic acid, a (meth) acrylate ester, and the like. Examples of the resin include alkali-soluble resins containing a polymerizable unsaturated group obtained by: copolymerizing (meth) acrylates comprising glycidyl (meth) acrylate in a solvent to obtain a copolymer, reacting (meth) acrylic acid with the obtained copolymer, and finally reacting the anhydride of the di-or tri-carboxylic acid. The copolymers can be referred to: a copolymer comprising 20 to 90 mol% of repeating units derived from diglycerol obtained by esterifying hydroxyl groups at both ends with (meth) acrylic acid and 10 to 80 mol% of repeating units derived from one or more polymerizable unsaturated compounds copolymerizable with the repeating units, having a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120mgKOH/g, as disclosed in Japanese patent laid-open No. 2014-111722; and a polymerizable unsaturated group-containing alkali-soluble resin which is a polymer comprising a unit derived from a (meth) acrylate compound and a unit having a (meth) acryloyl group and a dicarboxylic acid residue or a tricarboxylic acid residue, and which has a weight average molecular weight (Mw) of 3000 to 50000 and an acid value of 30 to 200mgKOH/g, as described in Japanese patent laid-open No. 2018-141968.
The unsaturated group-containing photosensitive resin of component (a) may be used alone or in combination of two or more.
(B) component (A)
Examples of the photopolymerizable monomer having at least two or more unsaturated bonds as the component (B) in the present embodiment include: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide-modified hexa (meth) acrylate of phosphazene, ethylene oxide-modified hexa (meth) acrylate of phosphazene, acrylonitrile-styrene-acrylate copolymer, and mixtures thereof, And (meth) acrylates such as caprolactone-modified dipentaerythritol hexa (meth) acrylate, and dendrimers having a (meth) acryloyl group as compounds having an ethylenic double bond. Only one kind of these monomers may be used alone, or two or more kinds may be used in combination. The photopolymerizable monomer having at least two ethylenically unsaturated bonds can function to crosslink molecules of the contained alkali-soluble resin, and in order to function, it is preferable to use a photopolymerizable monomer having three or more unsaturated bonds. Further, the acrylic acid equivalent obtained by dividing the molecular weight of the monomer by the number of (meth) acrylic acid groups in one molecule is preferably 50 to 300, and more preferably 80 to 200. The component (B) has no free carboxyl group.
Examples of the compound having an unsaturated bond which can be contained in the composition as the component (B) include a dendritic polymer having a (meth) acryloyl group: a dendritic polymer obtained by adding a polyvalent mercapto compound to a part of carbon-carbon double bonds in a (meth) acryloyl group of a polyfunctional (meth) acrylate. Specifically, the method comprises the following steps: and a dendritic polymer obtained by reacting a (meth) acryloyl group of a polyfunctional (meth) acrylate represented by the following general formula (3) with a polyvalent mercapto compound represented by the following general formula (4).
[ solution 3]
Figure BDA0003138481910000071
(in the formula (3), R5Is a hydrogen atom or a methyl group, R6To be R7(OH)kN hydroxyl groups of the k hydroxyl groups of (a) are supplied to the remaining part after ester bonding in the formula; as preferred R7(OH)kA polyol having a C2-8 nonaromatic linear or branched hydrocarbon skeleton, a polyol ether having a plurality of molecules of the polyol linked to each other via an ether bond by dehydration condensation of the alcohol, or an ester of the polyol or the polyol ether and a hydroxy acid; k and n independently represent an integer of 2 to 20, k is not less than n)
[ solution 4]
Figure BDA0003138481910000081
(in the formula (4), R8Is a single bond or a C1-6 hydrocarbon group having a valence of 2 to 6, m is R8Is a single bond, is 2 at R8When it is a 2-to 6-valent radical and R8Equal in price)
Examples of the polyfunctional (meth) acrylate represented by the general formula (3) include: (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified pentaerythritol tri (meth) acrylate. These compounds may be used alone or in combination of two or more.
Examples of the polyvalent mercapto compound represented by general formula (4) include: trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tris (mercaptoacetate), pentaerythritol tetrakis (mercaptopropionate), dipentaerythritol hexa (mercaptoacetate), dipentaerythritol hexa (mercaptopropionate), and the like. These compounds may be used alone or in combination of two or more.
(A) The blending ratio of the component (A) to the component (B) is preferably 30/70 to 90/10, more preferably 60/40 to 80/20 in terms of the weight ratio (A)/(B). When the blending ratio of the component (A) is 30/70 or more, the cured product after photo-curing is less likely to become brittle, and the acid value of the coating film is less likely to decrease in the unexposed portion, so that the decrease in solubility in an alkaline developer can be suppressed. Therefore, problems such as jagged pattern edges or unclear pattern edges are not likely to occur. When the blending ratio of the component (a) is 90/10 or less, the ratio of the photoreactive functional group in the resin is sufficient, and thus a desired crosslinked structure can be formed. Further, since the acid value of the resin component is not excessively high, the solubility of the exposed portion in an alkaline developer is not likely to be high, and thus, the pattern formed can be suppressed from becoming thinner than the target line width or from missing.
Component (C)
Examples of the photopolymerization initiator as the component (C) in the present embodiment include: acetophenones such as acetophenone, 2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone and p-tert-butyl acetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, p' -bisdimethylaminobenzophenone; benzoin ethers such as benzil, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like; biimidazole compounds such as 2- (o-chlorophenyl) -4, 5-phenylbiimidazole, 2- (o-chlorophenyl) -4, 5-bis (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4, 5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4, 5-diphenylbiimidazole, and 2, 4, 5-triarylbiimidazole; halomethylthiazole compounds such as 2-trichloromethyl-5-styryl-1, 3, 4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1, 3, 4-oxadiazole and 2-trichloromethyl-5- (p-methoxystyryl) -1, 3, 4-oxadiazole; 2, 4, 6-tris (trichloromethyl) -1, 3, 5-triazine, 2-methyl-4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- (4-chlorophenyl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- (4-methoxystyryl) -4, 6-bis (trichloromethyl) -1, halogenated methyl-s-triazine compounds such as 3, 5-triazine, 2- (3, 4, 5-trimethoxystyryl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, and 2- (4-methylthiostyryl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine; 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -, o-acyloxime-based compounds such as 2- (O-benzoyloxime), 1- (4-phenylthiophenyl) butane-1, 2-dione-2-oxime-O-benzoate, 1- (4-methylthiophenyl) butane-1, 2-dione-2-oxime-O-acetate, 1- (4-methylthiophenyl) butane-1-ketoxime-O-acetate, and 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazol-3-yl-O-acetyloxime; sulfur compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothianthrone, 2, 4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, and 2, 3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, etc.; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole; tertiary amines such as triethanolamine and triethylamine, and the like. These photopolymerization initiators may be used alone or in combination of two or more.
Examples of the group of O-acyloxime-based compounds that can be preferably used include O-acyloxime-based photopolymerization initiators represented by the following general formula (5) and the following general formula (6). In the compound group, when the light-shielding component is used at a high concentration, it is preferable to use an O-acyloxime-based photopolymerization initiator having a molar absorption coefficient of 10000 or more at 365 nm. In the present invention, the "photopolymerization initiator" is used as meaning including a sensitizer.
[ solution 5]
Figure BDA0003138481910000101
(in the formula (5), R9、R10Each independently represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 4 to 12 carbon atoms, R11Represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms; here, the alkyl group and the aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or a halogen, and the alkylene group may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond; further, the alkyl group may be any of a linear, branched, or cyclic alkyl group)
[ solution 6]
Figure BDA0003138481910000102
(in the formula (6), R12And R13Each independently is a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl, cycloalkylalkyl or alkylcycloalkyl group having 4 to 10 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms; r14Each independently is a C2-10 linear or branched alkyl or alkenyl group, wherein-CH in the alkyl or alkenyl group2A part of the radicals may be substituted by-O-radicals; further, these R' s12～R14A part of hydrogen atoms in the group (2) may be substituted with halogen atoms)
(C) The amount of the photopolymerization initiator of component (B) is preferably 3 to 30 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the total of the components of component (a) and component (B). When the component (C) is blended in an amount of 3 parts by weight or more, the sensitivity is good and a sufficient photopolymerization rate can be obtained. When the blending ratio of the component (C) is 30 parts by weight or less, a desired pattern line width and a desired pattern edge can be obtained because of appropriate sensitivity.
(D) component
The light-shielding component such as the black pigment, the mixed-color organic pigment, and the light-shielding material as the component (D) in the present embodiment is a component dispersed in an average particle diameter of 1 to 1000nm (average particle diameter measured by a particle diameter distribution meter by a laser diffraction/scattering method or a particle diameter distribution meter by a dynamic light scattering method), and a known light-shielding component can be used without particular limitation.
Examples of the black pigment as the (D) component include: perylene black, cyanine black, aniline black, lactam black, carbon black, titanium black, and the like.
Examples of the mixed color organic pigment as the (D) component include: a pigment obtained by mixing at least two colors selected from organic pigments such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, vat (threne) pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, thioindigo pigments, and the like.
Depending on the function of the intended photosensitive resin composition, the component (D) may be used alone or in combination of two or more.
Examples of the organic pigment that can be used when the mixed Color organic pigment is used as the component (D) include, but are not limited to, pigments identified by the Color Index (Color Index) name as follows.
Pigment Red (pigment red)2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, and the like
Pigment orange (pigment orange)5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81 and the like
Pigment yellow (pigment yellow)1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc
Pigment Green 7, 36, 58, etc
Pigment blue (pigment blue)15, 15: 1. 15: 2. 15: 3. 15: 4. 15: 6. 16, 60, 80, etc
Pigment Violet 19, 23, 37, and the like
The blending ratio of the light-shielding component of the component (D) may be arbitrarily determined according to the desired light-shielding degree, and is preferably 20 mass% or more and 80 mass% or less, and more preferably 40 mass% or more and 70 mass% or less with respect to the solid component in the photosensitive resin composition. When an organic pigment such as aniline black, cyanine black, or lactam black, or a carbon-based light-shielding component such as carbon black is used as the light-shielding component of component (D), it is particularly preferably 40 mass% or more and 60 mass% or less with respect to the solid content in the photosensitive resin composition. When the light-shielding component is 20% by mass or more relative to the solid content in the photosensitive resin composition, sufficient light-shielding properties can be obtained. If the light-shielding component is 80 mass% or less with respect to the solid content in the photosensitive resin composition, the content of the photosensitive resin that originally becomes the binder is not reduced, and therefore, desired development characteristics and film forming ability can be obtained.
The component (D) is usually mixed with other formulating components in the form of a light-screening component dispersion dispersed in a solvent, and in this case, a dispersant may be added. The dispersant may be any known compound used for dispersing a pigment (light-shielding component) (e.g., a compound commercially available under the names of a dispersant, a dispersing wetting agent, and a dispersion accelerator).
Examples of dispersants include: a cationic polymer dispersant, an anionic polymer dispersant, a nonionic polymer dispersant, and a pigment derivative type dispersant (dispersing aid). In particular, the dispersant is preferably a cationic polymer dispersant having a cationic functional group such as an imidazole group, a pyrrole group, a pyridine group, a primary amino group, a secondary amino group or a tertiary amino group, an amine value of 1mgKOH/g to 100mgKOH/g, and a number average molecular weight (Mn) of 1000 to 100000, in terms of adsorption to a colorant. The amount of the dispersant blended is preferably 1 to 35% by mass, more preferably 2 to 25% by mass, based on the light-shielding component. Resin-based high-viscosity substances generally have an action of stabilizing dispersion, but substances having no dispersion-accelerating ability are not treated as dispersants. However, the case of using for the purpose of stabilizing the dispersion is not limited.
Further, (E) the total mass (m) of silica particles (described later)E) Relative to the total mass (m) of the (D) light-shielding componentD) Ratio (m)E/mD) Preferably 0.01 to 0.20, more preferably 0.05 to 0.1. If (E) the total mass (m) of the silica particlesE) Relative to the total mass (m) of the light-shielding component (D)D) The ratio of (b) is in the above range, both high light-shielding property and low reflectance can be achieved.
Component (E)
The silica particles as the component (E) are not particularly limited in terms of the production method such as gas phase reaction or liquid phase reaction, or the shape (spherical or non-spherical).
The type of the silica particles used as the component (E) in the present invention is not particularly limited. Solid silica may be used, as may hollow silica particles. The "hollow silica particles" mean silica particles having a cavity inside the particles.
By using the silica particles, the refractive index of the light-shielding film containing the silica particles can be reduced.
The average particle diameter of the silica particles is preferably 1nm to 100nm, more preferably 10nm to 90 nm. It is considered that when the average particle diameter is within the above range, aggregation of silica particles is less likely to occur, as compared with the case of a small particle diameter such as a few nanometers (nm). Thus, the silica particles have excellent dispersion stability in the particle diameter range, and can be uniformly present in the light-shielding film. Therefore, the reflectance of the light-shielding film is less likely to vary.
The content of the silica particles is preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass, based on the total mass of the photosensitive resin composition. When the content of the silica particles is within the above range, a low reflectance can be achieved and a good photo-patterning property can be secured.
The average particle diameter of the silica particles can be measured by an accumulation method using a particle size distribution meter "particle diameter Analyzer FPAR-1000" (manufactured by Otsuka electronics Co., Ltd.) by a dynamic light scattering method.
In addition, the silica particles can use particles with a refractive index of 1.10-1.47. By using hollow silica particles having a low refractive index in addition to the particles having a refractive index of 1.45 to 1.47 of the ordinary silica particles, the refractive index of the light-shielding film can be further reduced as compared with the refractive index of the light-shielding film including only the ordinary silica particles.
The refractive index of the silica particles can be determined from a transparent mixed solution obtained by mixing the silica particles processed into a powder with a standard refractive liquid having a known refractive index. In this case, the refractive index of the standard refractive liquid of the mixed liquid is set to the refractive index of the silica particles. The refractive index of the silica particles can be measured using an Abbe (Abbe) refractometer.
In addition, since reflection due to a difference in refractive index between the transparent substrate and the light-shielding film formed can be suppressed, reflection can be suppressed without providing an antireflection film or the like separately on the substrate.
The shape of the silica particles may be spherical or elliptical. The shape of the silica particles used in the present invention is preferably spherical.
The sphericity of the silica particles is preferably 1.0 to 1.5. If the sphericity of the silica particles is in the above range, the particle shape is close to a sphere. Therefore, the light-shielding film can be filled homogeneously with a thin film thickness, and the light-shielding film can be formed without exposing the silica particles from the film surface to the outside while maintaining the smoothness of the film surface. Therefore, a light-shielding film having a low refractive index and sufficient strength can be obtained.
The sphericity of the silica particles can be determined from the ratio of the longest diameter to the shortest diameter of the particles (average value of arbitrary 100 silica particles). Here, the longest diameter and the shortest diameter of the silica particles are values obtained by taking an image of the silica particles with a transmission electron microscope and measuring the longest diameter and the shortest diameter of the silica particles from the obtained photomicrograph.
The silica particles as the component (E) may be mixed with other compounding ingredients as a silica particle dispersion dispersed in a solvent. The dispersant may be any known compound used for dispersing a pigment (light-shielding component) (e.g., a compound commercially available under the names of a dispersant, a dispersing wetting agent, and a dispersion accelerator). In the present embodiment, the silica particle dispersion contains a dispersant (F) described later.
(F) component
The dispersant as the component (F) in the present embodiment has an acid value and an amine value, and both the acid value and the amine value are 10mgKOH/g to 80 mgKOH/g. When the amine value of the dispersant is 10mgKOH/g or more, the dispersibility of the silica particles can be improved. On the other hand, a dispersant having only an amine value improves the dispersibility of silica particles, but reduces the solubility of silica particles in a developer, and therefore remains as a residue at the edge of a pattern, thereby reducing the linearity. On the other hand, when the amine value of the dispersant is not less than 10mgKOH/g and the acid value is also not less than 10mgKOH/g, the dispersibility of the silica particles can be improved and a high-definition pattern can be formed. On the other hand, by setting both the acid value and the amine value to 80mgKOH/g or less, it is possible to suppress a decrease in the fineness of the formed pattern without excessively increasing the solubility of the silica particles protected by the dispersant in the developer. From the above viewpoint, the amine value and the acid value of the dispersant are preferably both 30mgKOH/g or more and 80mgKOH/g or less, and more preferably both 30mgKOH/g or more and 80mgKOH/g or less.
Further, the dispersibility of the silica particles can be improved, and the generation of aggregated foreign matter derived from the silica particles can be suppressed. The acid value of the dispersant as the component (F) is the number of mg of KOH required for neutralizing 1g of the resin component (solid content), and can be measured in accordance with Japanese Industrial Standard (JIS) -K0070. The amine value of the dispersant as the component (F) means the equivalent amount of KOH mg relative to the amount of an acid (acetic acid or the like) required for neutralizing 1g of the resin component (solid content), and can be measured in accordance with JIS-K7237.
Examples of the dispersant as the component (F) include: alkyl ammonium salts and alkanol ammonium salts of acidic polymers, alkyl ammonium salts and alkanol ammonium salts of polymer copolymers having an acid group, neutralized salts of polymers having an alkylamino group, phosphate ester salts of polymer copolymers, and the like. Among these, preferred are alkylammonium salts of acidic polymers or alkylammonium salts of high-molecular copolymers having acidic groups. By using an alkyl ammonium salt or an alkanol ammonium salt of an acidic polymer or an alkyl ammonium salt or an alkanol ammonium salt of a polymer copolymer having an acid group as a dispersant, generation of aggregated foreign matter derived from the silica particles can be more significantly suppressed.
Examples of commercially available dispersants as component (F) include: DISPERBYK 140, 142, 145, 2001, 2025, 9076 (all manufactured by BYK-Chemie Japan) corporation, "DISPERBYK" is a registered trademark of BYK-Chemie Japan corporation) and the like. Among the commercially available products, Diepbick (DISPERBYK) -140, 142, 9076 is preferable, and Diepbick (DISPERBYK) -140, 9076 is more preferable.
(F) The content of the dispersant is preferably 0.01 to 0.5 parts by mass based on the total mass of the photosensitive resin composition.
Further, the total mass (m) of the dispersant (F)F) Relative to the total mass (m) of the (E) silica particlesE) Ratio (m)F/mE) Preferably 0.02 to 0.6, more preferably 0.03 to 0.4. If the total mass (m) of the dispersant (F)F) Relative to the total mass (m) of the silica particlesE) When the ratio of (b) is in the above range, the reflectance on the glass substrate side can be reduced, and the generation of aggregated foreign matter derived from silica particles can be suppressed.
The dispersion liquid used in the photosensitive resin composition of the present invention can be prepared by mixing and dispersing the components (a) to (F) by an appropriate method.
7. Solvent(s)
In the photosensitive resin composition of the present invention, it is preferable to use a solvent as the component (G) in addition to the components (a) to (F). Examples of the solvent include: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α -terpineol and β -terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and acetates such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These compounds may be used alone or in combination of two or more kinds thereof, and dissolved and mixed to prepare a uniform solution composition.
The photosensitive resin composition of the present invention may optionally contain additives such as a resin other than the component (a) such as an epoxy resin, a curing agent, a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler other than silica, a leveling agent, an antifoaming agent, a surfactant, and a coupling agent.
Examples of the thermal polymerization inhibitor and the antioxidant include: hydroquinone, hydroquinone monomethyl ether, pyrogallol (pyrogallol), t-butyl catechol, phenothiazine, hindered phenol compounds, and the like. Examples of plasticizers include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of the filler material include: glass fibers, silica, mica, alumina, and the like. Examples of defoaming or leveling agents include: silicone, fluorine, and acrylic compounds. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and the like. Examples of coupling agents include: 3- (glycidyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, etc.
The photosensitive resin composition of the present invention preferably contains, in a solid component excluding a solvent (the solid component contains a monomer which becomes a solid component after being cured by light), a photosensitive resin containing an unsaturated group as the component (a), a photopolymerizable monomer having at least two unsaturated bonds as the component (B), a photopolymerization initiator as the component (C), at least one light-shielding component selected from a black pigment, a color mixing pigment and a light-shielding material as the component (D), silica particles (E), and a dispersant (F). The amount of the solvent varies depending on the target viscosity, and is preferably 40 to 90% by mass based on the whole amount.
The photosensitive resin composition of the present invention can be produced by mixing (a) an unsaturated group-containing photosensitive resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, a light-shielding component dispersion in which (D) a light-shielding component is dispersed in a solvent, and a silica particle dispersion in which (E) silica particles are dispersed in a solvent. The silica particle dispersion (E) contains the dispersant (F).
By previously containing (F) a dispersant in (E) the silica particle dispersion, the dispersion stability of the silica dispersion can be improved, and the generation of aggregated foreign matter can be prevented when mixing with other resin components.
The light-shielding film obtained by curing the photosensitive resin composition of the present invention can be obtained, for example, by: a solution of the photosensitive resin composition is applied to a substrate or the like, the solvent is dried, and the substrate is cured by irradiation with light (including ultraviolet rays, radiation rays, and the like). A desired pattern can be obtained by providing a portion irradiated with light and a portion not irradiated with light using a photomask or the like, hardening only the portion irradiated with light, and dissolving the other portion with an alkaline solution.
Further, a color filter or a touch panel having the light-shielding film of the present invention as a black matrix can be manufactured, for example, by: forming a light-shielding film having a film thickness of 1.0 to 2.0 μm on a transparent substrate, and forming red, blue and green pixels by photolithography after the formation of the light-shielding film; in addition, red, blue, and green inks are injected into the light-shielding film by an ink-jet process.
Further, the light-shielding film obtained by curing the photosensitive resin composition of the present invention can be used as a black columnar spacer of a liquid crystal display device. For example, a single black resist may be used to form a plurality of portions having different thicknesses, one of which functions as a spacer and the other of which functions as a black matrix.
The respective steps of the method for forming a light-shielding film by applying and drying a photosensitive resin composition are specifically exemplified.
As a method for applying the photosensitive resin composition to a substrate, any of known methods such as a solution dipping method, a spraying method, a method using a roll coater, a disc coater (Land coater machine), a slit coater, and a rotary coater can be used. After coating to a desired thickness by these methods, the coating film is formed by removing the solvent (prebaking). The prebaking is performed by heating with an oven, a hot plate, or the like, vacuum drying, or a combination of these. The heating temperature and the heating time in the prebaking may be appropriately selected depending on the solvent used, and are preferably, for example, from 1 minute to 10 minutes at 80 ℃ to 120 ℃.
As the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like can be used, and the wavelength range of the radiation is preferably 250nm to 450 nm. As a developer suitable for the alkali development, for example, an aqueous solution of sodium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, or the like can be used. These developing solutions may be appropriately selected depending on the characteristics of the resin layer, but it is also effective to add a surfactant as necessary. The developing temperature is preferably 20 to 35 ℃, and a fine image can be formed precisely using a commercially available developing machine, ultrasonic cleaner, or the like. After the alkali development, water washing is usually performed. As the developing method, a shower developing method, a spray developing method, a dip (dip) developing method, a puddle (paddle) developing method, or the like can be applied.
After the development, heat treatment (post-baking) is performed at 180 to 250 ℃ for 20 to 100 minutes. The post baking is performed for the purpose of improving adhesion between the patterned light-shielding film and the substrate. This can be performed by heating with an oven, a hot plate, or the like, as in the case of the prebaking. The patterned light-shielding film of the present invention is formed through each step by photolithography. Further, polymerization or curing (which may be collectively referred to as curing) is completed by heat, whereby a light-shielding film having a desired pattern can be obtained.
As described above, the photosensitive resin composition for a black resist of the present invention is suitable for forming a fine pattern by an operation such as exposure and alkali development, and can also provide a light-shielding film having excellent light-shielding properties, adhesion, electrical insulation properties, heat resistance, and chemical resistance even when a pattern is formed by conventional screen printing.
The photosensitive resin composition for a black resist of the present invention can be suitably used as a coating material. In particular, an ink for a color filter used in a liquid crystal display device or an imaging element, and a light-shielding film formed from the ink are useful as a color filter, a black matrix for liquid crystal projection, and the like. The photosensitive resin composition for a black resist of the present invention can be used as an ink material for dividing or shielding light of each color in various multicolor displays such as an organic Electroluminescence (EL) device, a color liquid crystal display device, a color facsimile, and an image sensor, in addition to a color filter ink for a color liquid crystal display. According to the color filter of the present invention, reflection of external light at the interface between the colored layer (including the black resist layer) and the substrate, or reflection of light emission from the element when used in an organic EL element, for example, can be reduced. That is, the bright contrast can be improved by reducing the reflection of external light, or the light emission efficiency can be improved by improving the light extraction efficiency from the light emitting side.
[ examples ]
Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these examples and comparative examples. In the present invention, when the first decimal place is 0, the content of each component may be omitted.
First, a description will be given of synthetic examples of an alkali-soluble resin containing an unsaturated group as the component (a), and evaluation of the resin in these synthetic examples is performed as follows unless otherwise described.
[ solid content concentration ]
A glass filter was impregnated with 1g of the resin solution obtained in synthesis example [ weight: w0(g) And weighed [ W ]1(g) Based on the weight [ W ] of the steel sheet after heating at 160 ℃ for 2 hours2(g) And is obtained by the following formula.
The solid content concentration (wt%) was 100 × (W)2-W0)/(W1-W0)
[ acid value ]
The resin solution was dissolved in dioxane and titrated with 1/10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Pongan industries, Ltd.).
[ molecular weight ]
Gel Permeation Chromatography (GPC) "HLC-8220 GPC" (manufactured by Tosoh corporation, Tosoh, Inc., solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2) + TSKgelSuper H-3000 (1) + TSKgelSuper H-4000 (1) + TSKgelSuper H-5000 (1) (manufactured by Tosoh corporation, Tosoh), temperature: 40 ℃, speed: 0.6ml/min) was used for measurement, and the weight average molecular weight (Mw) was determined as a conversion value of standard polystyrene (manufactured by Tosoh, Inc., PS-oligomer kit).
[ average particle diameter ]
The average particle diameter of the silica particles was determined by an accumulation method using a particle size distribution analyzer "particle diameter Analyzer FPAR-1000" (manufactured by Otsuka electronics Co., Ltd.) by a dynamic light scattering method.
The abbreviations used in the synthesis examples and comparative synthesis examples are as follows.
BPFE: bisphenol fluorene type epoxy compound (reaction product of 9, 9-bis (4-hydroxyphenyl) fluorene and chloromethyl oxetane, wherein in the compound of general formula (1), X is fluorene-9, 9-diyl and R1～R4Compounds which are hydrogen)
AA: acrylic acid
BPDA: 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride
THPA: tetrahydrophthalic anhydride
TEAB: tetraethylammonium bromide
PGMEA: propylene glycol monomethyl ether acetate
[ Synthesis examples ]
BPFE (114.4g, 0.23 mol), AA (33.2g, 0.46 mol), PGMEA (157g) and TEAB (0.48g) were put into a 500ml four-necked flask equipped with a reflux condenser, and the mixture was stirred at 100 ℃ to 105 ℃ for 20 hours to react. Then, BPDA (35.3g, 0.12 mol) and THPA (18.3g, 0.12 mol) were put into the flask, and stirred at 120 to 125 ℃ for 6 hours to obtain an alkali-soluble resin (A) containing an unsaturated group. The resin solution thus obtained had a solid content of 56.0% by mass, an acid value (in terms of solid content) of 103mgKOH/g, and Mw of 3600 as determined by GPC analysis.
Photosensitive resin compositions of examples 1 to 10 and comparative examples 1 to 7 were prepared in the blending amounts (unit is mass%) shown in table 1. The formulation ingredients used in table 1 are as follows.
(alkali-soluble resin having unsaturated group)
(A) The method comprises the following steps The unsaturated group-containing alkali-soluble resin solution (solid content concentration 56.0 mass%) obtained in the above synthesis example
(photopolymerizable monomer)
(B) The method comprises the following steps A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Aronix M-405, manufactured by east Asia synthetic Co., Ltd., "Aronix" is a registered trademark of east Asia synthetic Co., Ltd.)
(photopolymerization initiator)
(C) -1: ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime) (Irgacure) OXE-02 manufactured by BASF Japan, Irgacure being a registered trademark of BASF Japan)
(C) -2: adeka arkls NCI-831 manufactured by Adeka corporation, "Adeka arkls" is a registered trademark of Adeka corporation
(carbon Black Dispersion)
(D) The method comprises the following steps PGMEA dispersion (solid content: 35.0% by mass) of a dispersion resin (alkali-soluble resin (A) (solid content: 8.0% by mass) in synthetic example) having a carbon black concentration of 25.0% by mass and a polymer dispersant concentration of 2.0% by mass
(E) The method comprises the following steps PGMEA dispersion of silica particles "YA 050C" (manufactured by Edmantech, Admatech) having a solid content of 30 mass% and an average particle diameter of 50nm)
(dispersing agent)
(F) -1: dipabpeck (DISPERBYK) -140 (solid content concentration 52% by mass)
(F) -2: dipabpeck (DISPERBYK) -142 (solid content concentration 60 mass%)
(F) -3: dipabpeck (DISPERBYK) -9076 (solid content concentration of 100 mass%)
(F) -4: dipabpeck (DISPERBYK) -167 (solid content concentration 52 mass%)
(F) -5: dipabpeck (DISPERBYK) -170 (solid content concentration 30 mass%)
(F) -6: dipabpeck (DISPERBYK) -180 (solid content concentration 100 mass%)
(F) -7: dipabpeck (DISPERBYK) -9077 (solid content concentration of 100 mass%)
Further, (F) -1 to (F) -7 are manufactured by BYK-Chemie Japan, and "DISPERBYK" is a registered trademark of BYK-Chemie Japan.
Further, (F) -1 is a dispersant having an alkylammonium salt structure of an acidic polymer, (F) -2 is a phosphate dispersant of a polymer copolymer, (F) -3 is a dispersant having an alkylammonium salt structure of a polymer copolymer having an acid group, (F) -4 is a urethane dispersant, (F) -5 is a polymer dispersant having an acidic functional group, (F) -6 is an alkanolammonium salt dispersant of a copolymer containing an acid group, and (F) -7 is a polymer copolymer having an amine value.
(solvent)
(G) -1: propylene Glycol Monomethyl Ether Acetate (PGMEA)
(G) -2: cyclohexanone (ANON)
Figure BDA0003138481910000221
[ evaluation ]
A light-shielding film obtained by curing the photosensitive resin composition for black resist for evaluation was produced as follows.
(preparation of light-shielding film for evaluation)
Using a spin coater, the photosensitive resin compositions shown in Table 1 were applied to a film having a thickness of 1.2 μm after heat curing so as to give an illuminance of 1000mJ/cm at a wavelength of 254nm by irradiation with a low-pressure mercury lamp2The surface of a 125mm × 125mm glass substrate "# 1737" (manufactured by corning) corporation) (hereinafter referred to as "glass substrate") was cleaned with ultraviolet rays, and prebaked at 90 ℃ for 1 minute using a hot plate to prepare a light-shielding film. Then, the exposure gap is adjusted toA negative photomask having a thickness of 100 μm and a line/space of 10 μm/50 μm was coated on the dry light-shielding film, and the illuminance was 30mW/cm using i-ray2Is irradiated by an extra-high pressure mercury lamp at 50mJ/cm2The ultraviolet ray of (2) to perform a photo-curing reaction of the photosensitive portion.
Then, the light-shielding film after exposure was exposed to light at 25 ℃ and 1kgf/cm using a 0.04% potassium hydroxide solution2The development treatment was carried out for +10 seconds and +20 seconds from the development time (break time) BT at which the pattern began to appear, and then, 5kgf/cm2The unexposed portions of the light-shielding film were removed to form a light-shielding film pattern on the glass substrate, and the light-shielding film was subjected to main curing (post-baking) at 230 ℃ for 30 minutes using a hot air dryer, thereby obtaining light-shielding films for evaluation in examples 1 to 10 and comparative examples 1 to 7.
The light-shielding film for evaluation thus produced was evaluated for the following items.
[ evaluation of Pattern straightness ]
(evaluation method)
The 10 μm mask pattern after the final hardening (post-baking) was observed to have jagged edges by using an optical microscope and a Scanning Electron Microscope (SEM). The pattern linearity was evaluated in the BT +10 seconds and BT +20 seconds. Further, it is acceptable to set O or more.
(evaluation criteria)
O: the edge portion of the pattern was not confirmed to be jagged
And (delta): partially confirming that the edge portion of the pattern is jagged
X: the edge part of the pattern is confirmed to be jagged throughout the whole
[ evaluation of optical Density ]
(evaluation method)
The Optical Density (OD) of the light-shielding film for evaluation thus produced was determined using a Macbeth transmission densitometer. The film thickness of the light-shielding film formed on the substrate was measured, and the value obtained by dividing the value of the Optical Density (OD) by the film thickness was defined as OD/μm.
The Optical Density (OD) was calculated by the following formula (1).
Optical Density (OD) ═ log10T (1)
(T represents a transmittance)
[ evaluation of reflectance ]
(evaluation method)
The substrate with a light-shielding film prepared in the same manner as the light-shielding film for evaluation was measured for reflectance on the substrate (glass substrate) side at an incident angle of 2 ° using an ultraviolet-visible-infrared spectrophotometer "UH 4150" (manufactured by Hitachi High-Tech Science, inc.). Moreover, Δ or more is defined as pass.
(evaluation criteria)
O: the substrate with the light-shielding film has a substrate side reflectance of 5% or less
And (delta): the substrate with the light shielding film has a reflectance of more than 5% and less than 6%
X: the substrate with the light shielding film has a substrate side reflectance of 6% or more
[ evaluation of agglomerated foreign matter ]
(evaluation method)
The light-shielding film for evaluation after the main curing (post-baking) was observed with an optical microscope to confirm the presence or absence of agglomerated foreign matter. Moreover, Δ or more is defined as pass.
(evaluation criteria)
O: no agglomerated foreign matter was observed in the light-shielding film
And (delta): condensed foreign matter was observed in a part of the light-shielding film
X: the aggregated foreign matter was observed over the entire surface of the light-shielding film
The evaluation results are shown in table 2.
Figure BDA0003138481910000251
As shown in examples 1 to 10, it was found that a high-definition pattern can be formed by using a dispersant having an acid value and an amine value of 10mgKOH/g or more and 80mgKOH/g or less. On the other hand, it was found that when both the acid value and the amine value were more than 80mgKOH/g, the solubility in the developer was too high, and the linearity of the pattern was deteriorated.
As shown in examples 1 to 10, it was found that the edge portions of the pattern were not jagged as compared with comparative examples 2 and 5 in which a dispersant having only an amine value was used. The reason is considered to be that: the solubility in the developer tends to be reduced by adsorbing the dispersant to the silica particles, but the solubility of the silica particles in the developer is ensured by applying a dispersant having an acid value and an amine value.
Further, as shown in examples 1 to 10, it was found that the dispersion stability of silica particles can be improved and the generation of aggregated foreign matter can be suppressed by using a dispersant having an acid value and an amine value of 10mgKOH/g or more and 80mgKOH/g or less. In particular, it was found that in examples 1 and 3 to 10 in which a polymer dispersant having an alkylammonium salt structure was used, the foreign matter derived from the aggregation of silica particles was significantly suppressed. The reason is considered to be that: the dispersant effectively protects silanol groups present on the surface of silica particles, and improves the dispersion stability in the photosensitive composition for black resists.
As shown in examples 1 to 10, it was found that the total mass (m) of the dispersant was measured by mixing (F)F) Relative to (E) the total mass (m) of the silica particlesE) Ratio (m)F/mE) The reflectance of the glass substrate side is suppressed to 5% or less and the aggregation of foreign matter derived from the silica particles is suppressed to 0.02 to 0.6. If mF/mEIf the amount is less than the above range, the dispersion stability of the silica particles is insufficient, and aggregated foreign matter is generated. On the other hand, if mF/mEIf the refractive index is larger than the above range, the compatibility of the silica particles is too high, and therefore the refractive index is not biased to the vicinity of the glass substrate, and the refractive index of the glass substrate side is larger than 5%.
[ industrial applicability ]
According to the photosensitive resin composition of the present invention, a photosensitive resin composition for a black matrix having both high light-shielding property and low reflectance, and a light-shielding film, a color filter, and a touch panel using the same can be provided. Further, according to the color filter and the touch panel, various display devices having excellent visibility can be provided.

Claims (10)

1. A photosensitive resin composition for a black resist, comprising:
(A) a photosensitive resin containing an unsaturated group;
(B) a photopolymerizable monomer having at least two or more unsaturated bonds;
(C) a photopolymerization initiator;
(D) at least one light-shielding component selected from the group consisting of black pigments, color-mixed pigments, and light-shielding materials;
(E) silica particles; and
(F) a dispersant which is a mixture of a dispersant and a surfactant,
the dispersant (F) has an acid value and an amine value, both of which are 10mgKOH/g or more and 80mgKOH/g or less, and the total mass m of the dispersant (F)FRelative to the total mass m of the (E) silica particlesERatio m ofF/mE0.02 to 0.60.
2. The photosensitive resin composition for a black resist according to claim 1, wherein the unsaturated group-containing photosensitive resin (A) is an unsaturated group-containing photosensitive resin obtained by reacting an epoxy compound having two glycidyl ether groups derived from a bisphenol represented by the following general formula (1) with a reaction product of (meth) acrylic acid and further with a polycarboxylic acid or an anhydride thereof,
Figure FDA0003138481900000011
in the formula (1), R1、R2、R3And R4Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and X represents-CO-, -SO2-、-C(CF3)2-、-Si(CH3)2-、-CH2-、-C(CH3)2-, -O-, a fluorene-9, 9-diyl group represented by the general formula (2) or a single bond, l is an integer of 0 to 10;
Figure FDA0003138481900000012
3. the photosensitive resin composition for a black resist according to claim 1 or 2, wherein the (F) dispersant is a polymer compound having an alkylammonium salt structure.
4. The photosensitive resin composition for a black resist according to claim 1 or 2, wherein the average particle diameter of the (E) silica particles is 1nm to 100 nm.
5. The photosensitive resin composition for black resist according to claim 1 or 2, wherein the total mass m of the (E) silica particlesERelative to the total mass m of the (D) light-shielding componentDRatio m ofE/mD0.01 to 0.20.
6. A process for producing a photosensitive resin composition for a black resist, which comprises subjecting a photosensitive resin composition to a treatment with a reducing agent
(A) A photosensitive resin containing an unsaturated group,
(B) A photopolymerizable monomer,
(C) A photopolymerization initiator,
(D) A light-shielding component dispersion obtained by dispersing a light-shielding component in a solvent, and
(E) silica particle dispersion obtained by dispersing silica particles in solvent
The components are mixed and then are mixed,
the silica particle dispersion (E) contains a dispersant (F),
the dispersant (F) has an acid value and an amine value, and the acid value and the amine valueAmine values of 10mgKOH/g or more and 80mgKOH/g or less, and the total mass m of the dispersant (F)FRelative to the total mass m of the (E) silica particlesERatio m ofF/mE0.02 to 0.60.
7. A light-shielding film obtained by curing the photosensitive resin composition for a black resist according to any one of claims 1 to 5.
8. A color filter having the light-shielding film according to claim 7 as a black matrix.
9. A touch panel having the light-shielding film according to claim 7 as a black matrix.
10. A display device having the color filter according to claim 8 or the touch panel according to claim 9.
CN202110731043.7A 2020-06-30 2021-06-29 Photosensitive resin composition for black resist, method for producing same, light-shielding film, color filter, touch panel, and display device Pending CN113867099A (en)

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