CN115903385A - Photosensitive resin composition, cured film, color filter, touch panel, and display device - Google Patents

Photosensitive resin composition, cured film, color filter, touch panel, and display device Download PDF

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Publication number
CN115903385A
CN115903385A CN202211189465.7A CN202211189465A CN115903385A CN 115903385 A CN115903385 A CN 115903385A CN 202211189465 A CN202211189465 A CN 202211189465A CN 115903385 A CN115903385 A CN 115903385A
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light
photosensitive resin
resin composition
acid
cured film
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Inventor
山田莉奈
小野悠树
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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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Priority claimed from JP2022135741A external-priority patent/JP2023051765A/en
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Publication of CN115903385A publication Critical patent/CN115903385A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention relates to a photosensitive resin composition, a cured film, a color filter, a touch panel and a display device. The invention provides a photosensitive resin composition, which can obtain a hardening film with expected light shielding performance and reflectivity and no burr generated at the edge part of a pattern in pattern formation. A photosensitive resin composition comprising: the light-shielding material comprises (A) a photosensitive resin containing an unsaturated group, (B) a photopolymerizable compound having at least two 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, and (E) fine particles having a refractive index of 1.50 to 1.80.

Description

Photosensitive resin composition, cured film, color filter, touch panel, and display device
Technical Field
The invention relates to a photosensitive resin composition, a cured film, a color filter, a touch panel and a display device.
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 which is one kind of light shielding film is provided on the liquid crystal panel to suppress light leakage from a screen at the time of black display and color mixture 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 black pigment concentration 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 characterized by comprising: hydrophobic silica fine particles and a specific dispersant (urethane dispersant). By using hydrophobic silica fine 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, the present inventors have studied and, as a result, the black photosensitive resin composition described in patent document 1 may not provide a light-shielding film having both desirable light-shielding properties and reflectance and causing no burrs at the pattern edge portions during pattern formation.
The present invention has been made in view of the above-described circumstances, and an object thereof is to provide a photosensitive resin composition having high light-shielding properties and low reflectance and capable of forming a high-definition pattern, a cured film obtained by curing the photosensitive resin composition, a color filter and a touch panel each having the cured film, and a display device having the color filter and the touch panel.
[ means for solving problems ]
That is, the gist of the present invention is as follows.
(1) A photosensitive resin composition comprising: the light-shielding material comprises (A) a photosensitive resin containing an unsaturated group, (B) a photopolymerizable compound having at least two 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, and (E) fine particles having a refractive index of 1.50 to 1.80.
(2) The photosensitive resin composition according to (1), wherein the fine particles (E) are alumina particles.
(3) The photosensitive resin composition according to (1) or (2), wherein the fine particles (E) have an average particle diameter of 10 to 300nm.
(4) The photosensitive resin composition according to any one of (1) to (3), wherein the proportion of the (E) fine particles in the solid content is 1 to 30% by mass.
(5) The photosensitive resin composition according to any one of (1) to (4), wherein a cured film having a film thickness of 1 μm obtained by curing the photosensitive resin composition by light has a light-shielding Optical Density (OD) [ μm ] -1 ]2.6 or more and the reflectance [% ] of the cured film]Is 6.5 or less, and the value obtained by dividing the reflectance of the cured film by the light-shielding degree OD is less than 1.65.
(6) A cured film obtained by curing the photosensitive resin composition according to any one of (1) to (5).
(7) A color filter having the cured film according to (6) as a black matrix.
(8) A touch panel having the cured film according to (6) as a black matrix.
(9) A display device having the color filter according to (7) or the touch panel according to (8).
[ Effect of the invention ]
The present invention provides a photosensitive resin composition capable of providing a cured film having high light-shielding properties and low reflectance, a cured film obtained by curing the photosensitive resin composition, a color filter and a touch panel each having the cured film, and a display device having the color filter and the touch panel.
Detailed Description
The present invention will be described in detail below.
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 developing alkali solubility 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 is characterized by reacting (meth) acrylic acid with an epoxy compound having two glycidyl ether groups derived from a bisphenol (hereinafter, also referred to as "bisphenol-type epoxy compound represented by 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 general formula (1). By using the bisphenol type epoxy compound represented by the general formula (1), good developing characteristics can be obtained.
[ solution 1]
Figure BDA0003868620990000031
In the formula (1), R 1 、R 2 、R 3 And R 4 Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and X represents-CO-, -SO 2 -、-C(CF 3 ) 2 -、-Si(CH 3 ) 2 -、-CH 2 -、-C(CH 3 ) 2 -, -O-, a fluorene-9, 9-diyl group represented by the general formula (2) or a single bond, and l is an integer of 0 to 10.
[ solution 2]
Figure BDA0003868620990000041
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-hydroxyphenyl) propane, bis (4-hydroxy-3, 5-dichlorophenyl) propane, bis (4-hydroxy-3, 2-hydroxyphenyl) propane, 2-bis (4-hydroxyphenyl) propane, 2-dichlorophenyl) propane, bis (4-hydroxy-3, 5-3, 2, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3, 5-dimethylphenyl) ether, bis (4-hydroxy-3, 5-dichlorophenyl) ether, 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, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene, 4 '-biphenol, 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. Examples of acid monoanhydrides of chain hydrocarbon dicarboxylic or tricarboxylic acids herein 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 such as 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 may be 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 includes 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 or more and 10.0 or less, 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 photo-patterning properties cannot be obtained, and therefore, it 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 its anhydride are not particularly limited, and known methods 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 200mgKOH/g. The weight average molecular weight (Mw) can be measured, for example, by Gel Permeation Chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh corporation). The acid value can be determined by titration with a 1/10N KOH aqueous solution using, for example, a potentiometric titrator "COM-1600" (manufactured by Ponga industries, ltd.).
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 a repeating unit derived from diglycerol obtained by esterifying hydroxyl groups at both ends with (meth) acrylic acid and 10 to 80 mol% of a repeating unit derived from one or more polymerizable unsaturated compounds copolymerizable with the repeating unit, 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 tricarboxylic acid residue, and has a weight average molecular weight (Mw) of 3000 to 50000 and an acid value of 30 to 200mgKOH/g, as disclosed in Japanese patent application laid-open No. 2018-141968.
(A) The content of the component (c) is preferably 10% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 80% by mass or less, based on the total mass of the solid components. When the content of the component (a) is 10% by mass or more, a high-resolution pattern can be formed.
The unsaturated group-containing photosensitive resin of component (a) may be used alone or in combination of two or more.
Examples of the photopolymerizable compound having at least two or more unsaturated bonds in the component (B) of the present embodiment include: (meth) acrylates such as 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, tripropylene glycol diacrylate, glycerin (meth) acrylate, glycerin 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, glycerin tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide-modified hexa (meth) acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like; (meth) acrylates having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; epoxy (meth) acrylates such as bisphenol a type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, bisphenol fluorene type epoxy (meth) acrylate, diphenylfluorene type epoxy (meth) acrylate, phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, phenol aralkyl type epoxy (meth) acrylate; and (meth) acrylic acid group-containing dendrimers as compounds having ethylenic double bonds. Only one kind of these photopolymerizable compounds may be used alone, or two or more kinds may be used in combination. The photopolymerizable compound having at least two ethylenically unsaturated bonds can function to crosslink molecules of the alkali-soluble resin having a polymerizable unsaturated group, and in order to function as such, it is preferable to use a photopolymerizable compound having three or more unsaturated bonds. The acrylic group equivalent obtained by dividing the molecular weight of the photopolymerizable compound by the number of (meth) acrylic groups in one molecule is preferably 50 to 300, and more preferably 80 to 200. The component (B) has no free carboxyl group.
(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, the pattern edge is less likely to be scratched or become unclear. 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. In addition, since the acid value of the resin component is not excessively high, the solubility of the exposed portion in the alkaline developer is not easily increased, and thus it is possible to suppress the formed pattern from becoming thinner than the target line width or from missing the pattern.
Examples of the photopolymerization initiator as the component (C) include: acetophenones such as acetophenone, 2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropylketone, dichloroacetophenone, trichloroacetophenone and p-tert-butylacetophenone; 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; halogenated methyl-s-triazines such as 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) -1,3, 5-triazine, 2- (3, 4, 5-trimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methylthiostyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine and the like; o-acyloxime-based compounds such as 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -,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 O-acyloxime-based compounds that can be preferably used include O-acyloxime-based photopolymerization initiators represented by general formulae (3) and (4). In the compound group, when the light-shielding component is used at a high concentration, it is also 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 3]
Figure BDA0003868620990000081
In the formula (3), R 5 、R 6 Each independently is C1-C15 alkyl, C6-C18 aryl, C7-C20 arylalkyl or C4-C12 heterocyclic radical, R 7 Is C1-C15 alkyl, C6-C18 aryl or C7-C20 arylalkyl. Here, the alkyl group and the aryl group may be substituted with a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 alkanoyl group, or a halogen, and the alkylene portion may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. The alkyl group may be any of linear, branched, and cyclic alkyl groups.
[ solution 4]
Figure BDA0003868620990000091
In the formula (4), R 8 And R 9 Each independently is a straight 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. R 10 Independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, wherein-CH is contained in the alkyl or alkenyl group 2 Part of the-groups may be substituted by-O-groups. Further, these R' s 8 ～R 10 A part of the hydrogen atoms in the group (2) may be substituted with halogen atoms.
(C) The amount of the photopolymerization initiator as 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 (a) and (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.
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 1nm 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 (D) component include, but are not limited to, the following pigments under the Color Index (Color Index) name.
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 and the like
Pigment Green 7, 36, 58, and the like
Pigment blue (pigment blue) 15, 15: 1. 15: 2. 15: 3. 15: 4. 15: 6. 16, 60, 80, etc
Pigment Violet (pigment violet) 19, 23, 37, etc
Of these, a black pigment is preferable, and carbon black is more preferable.
The average primary particle diameter of the carbon black is preferably 5nm or more and 60nm or less, more preferably 10nm or more and 50nm or less, and still more preferably 20nm or more and 45nm or less. In the present specification, the particle size or average primary particle size of the light-shielding component refers to an arithmetic average value of 1500 particles or primary particles of the light-shielding component with respect to an average value of a major diameter and a minor diameter obtained by observing the particles or primary particles of the light-shielding component with an electron microscope. The larger the average primary particle diameter of carbon black is, the more easily the carbon black is dispersed at a high concentration. By making the average primary particle diameter of the carbon black not excessively large, the shape defects of the secondary particles and the reduction in surface roughness can be suppressed.
Further, the dibutyl phthalate (DBP) oil absorption of the carbon black is preferably 100ml/100g or less. The DBP oil absorption is the capacity of dibutyl phthalate (DBP) absorbed by 100g of carbon black (Japanese Industrial Standards, JIS) K6217-4 (2017)). When the DBP oil absorption of the carbon black is in the above range, the electrical resistance value and the degree of blackness of the cured film can be further improved, and the decrease in coatability due to the increase in viscosity of the photosensitive resin composition can be suppressed.
The pH of the carbon black is preferably 2 or more and 10 or less, more preferably 5 or more and 9 or less, and still more preferably 4 or more and 8 or less. The pH value is a value measured by a glass electrode pH meter on a mixed solution of carbon black and distilled water. The higher the pH of the carbon black, the more stable the carbon black. By setting the pH of the carbon black within a range not too high, the adhesion of the cured film to the substrate can be further improved.
Further, ash content of carbon black is preferably 1.0% or less. If the ash content is 1.0% or less, the resistance value of the cured film can be further improved.
Further, the specific surface area of carbon black is preferably 20m 2 More than 300 m/g 2 The ratio of the carbon atoms to the carbon atoms is below g. If the specific surface area is 20m 2 When the ratio is greater than or equal to/g, the shape of the cured film is easily stabilized. If the specific surface area is 300m 2 The lower/g is preferable because the required amount of the dispersant, dye, etc. can be reduced, and the cost can be further reduced.
Further, the carbon black preferably has an acidic functional group on the surface thereof by oxidation treatment. It is particularly preferable that the surface has two or more acidic functional groups by a plurality of oxidation treatments. The acidic functional group can improve the dispersibility of the carbon black. Examples of the oxidation treatment include treatments using ozone gas, nitric acid, sodium hypochlorite, hydrogen peroxide, nitric oxide gas, nitrogen dioxide gas, sulfuric anhydride, fluorine gas, concentrated sulfuric acid, nitric acid, various peroxides, and the like. Examples of the acidic functional group include: hydroxyl group, pendant oxy group, hydroperoxy group, carbonyl group, carboxyl group, peroxycarboxylic acid group, aldehyde group, ketone group, nitro group, nitroso group, amide group, imide group, sulfonic acid group, sulfinic acid group, sulfenic acid group, thiocarboxylic acid group, chlorous acid group, perchloric acid group, iodous acid group, and the like.
The component (D) may be surface-treated by coating the surface with a dye. In particular, carbon black having a surface coated with a dye can improve the developability of the photosensitive resin composition, improve the adhesion of a cured film obtained by curing the photosensitive resin composition to a substrate, the fine line reproducibility and the light-shielding property, and improve the resistance value of the cured film.
The dye may be adsorbed on the surface of the light-screening component, and a basic dye, an acid dye, a direct dye, a reactive dye, or the like may be used. In addition, in this case, when an acidic functional group is provided (oxidized) on the surface of the light-shielding component (particularly, carbon black) in order to improve the dispersibility thereof, an acidic dye (particularly, an acidic dye having a sulfonic acid group or a carboxyl group) which easily interacts with the acidic functional group is preferable. From the viewpoint of suppressing the reaction with the acidic group contained in the component (a), an acidic dye or a nonionic dye is preferable to a dye having an amino group or the like. In addition, a dark-colored dye is preferable from the viewpoint of further improving the light-shielding property of the cured film.
Specific examples of the dye include: food color dyes such as Food Black (Food Black) No.1, food Black (Food Black) No.2, food Red (Food Red) No.40, food Blue (Food Blue) No.1, food Yellow (Food Yellow) No.7, and the like; bernard Red (bernard) 2BMN, bas Black (base Black) X34 (BASF X-34) (manufactured by BASF corporation), kayanol Red (Kayanol Red) 3BL (manufactured by Nippon Kayaku Company), demar carbon (dermocaron) 2GT (manufactured by Sandoz corporation), teflon Fast Yellow (Telon Fast Yellow) 4GL-175, bas Black (BASF base Black) SE 0228, bas Black (base Black) X34 (BASF X-34) (manufactured by BASF corporation), bas Blue (BASF Blue) 750 (BASF corporation), bernard Red (bernard) (manufactured by BASF corporation), bas Black (BASF y, manufactured by BASF corporation), bas Black (bash Black) 0228, bas Black (BASF Black) X34 (BASF X-34) (manufactured by BASF corporation); pontamine Brilliant bridge Blue (Pontamine Brilliant Bond Blue) A and other Pontamine Brilliant bridge Blue (Pontamine Bond Blue) A and other Pontamine (Pontamine) (registered trademarks) dyes (Pittsburgh Bayer chemical Corporation, pittsburgh, pa.), katasol Yellow GTF filter cake (Cartasol Yellow GTF Presscae) (mountain Deskz, inc. (Sandoz, manufactured by santoshi Inc), katasol Yellow GTF Liquid specialty (katasol Yellow GTF Liquid specialty) 110 (manufactured by Sandoz Inc., shang d., inc.), yellow Shade (Yellow Shade) 16948 (manufactured by trinken (Tricon), direct bright Pink (Direct bright Pink) B (manufactured by compton-nors (Crompton & Knowles)), karta Black (Carta Black) 2GT (manufactured by Sandoz Inc., sandoz., inc.), smith super Yellow (Sirius Yellow) GD 167, cartasol Brilliant Yellow (Cartasol Brilliant Yellow) 4GF (manufactured by Sandoz corporation), pagasol Yellow (Pergasol Yellow) CGP (manufactured by Ciba-Geigy corporation), pyrazole Black (Pyrazol Black) BG (manufactured by JCI corporation), diazole Black (Diazol Black) RN Quad (manufactured by JCJ corporation), pontamine Brilliant Blue (Pontamine Brilliant Bond Blue), berncarrel (Berncolor) A.Y.34; cibacron Brilliant Red 3B-A (Reactive Red 4) (manufactured by Milwaukee, wis.), driman Brilliant Red X-2B (Reactive Red 56) (manufactured by Aldrich Chemical, milwaukee, wis.), levax Brilliant Red E-4B (Reactive Red E-4B), levafix Brilliant Red E-4B, levafix Brilliant Red F-6BA and similar Livafix (Levafix) (registered trademark) L.P. Dyprodase:Sub>A dye (dye Stystar L.P.) (manufactured by Charlotte, north Americase:Sub>A Inc.), reactive Red CI (Reactive Red NC-4) (manufactured by Jerworkur Aldrich Chemical, milwaukee, wis.), reactive Red CI (Reactive Red NC-8, manufactured by Reynar NC-1, reynar NC-1B); niao Heteropenred (Neozapon Red) 492 (manufactured by BASF corporation), orasol Red (Orasol Red) G (Ciba-Geigy corporation), blue dyed Schilon Red (Aizen Spilon Red) C-BH (Hodogaya Chemical Company), spelin Fast Yellow (Spait Yellow) 3G, blue dyed Schilonghuang (Aizen Spilon Yelly) C-GNH (Hodogaya Chemical Company), orasol Black (Orasol Black) RL (Ciba-Geigy) Inc.), orasol Black (Orasol Black) RLP (Ciba-Geigy) Inc., sanxol Black (Sanxon Blacko Black) RLP (Ciba-Geigy) manufactured by Sanxon Black (Sanxon Black) Saybolt (Saybolt) Blaston Black (Ciba-Geigy) manufactured by Moaso, moaso Blue), moxol Black dye Concentrate S-Moraxel Blue (Moraxel Blue), and the like. These may be used alone or two or more of them may be used in combination.
The content of the dye is preferably 0.5% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 7% by mass or less, with respect to the total mass of the component (D). The larger the amount of the dye, the more the resistance value of the cured film can be increased. By setting the amount of the dye not to be excessive, the thickening of the photosensitive resin composition by the remaining dye and the generation of coagulation caused by the remaining dye interfering with the dispersibility of other components can be suppressed.
Alternatively, the dye may be laked by a metal or metal salt. By fixing the dye to the surface of the light-shielding component via the metal or metal salt after the dye is laked, the reduction of the effect due to the detachment of the dye from the light-shielding component can be suppressed. Examples of the metal include: aluminum, magnesium, calcium, strontium, barium, manganese, and the like. Examples of the metal salt include hydrochloride and sulfate salts of these metals and the like. The content of the metal or metal salt is preferably 0.3 times by mole or more, more preferably 0.5 times by mole, and still more preferably 0.8 times by mole with respect to the dye.
The blending ratio of the light-shielding component of the component (D) may be arbitrarily determined depending on the desired light-shielding degree, and is preferably 20 to 80% by mass, more preferably 40 to 70% by mass, based on the solid content 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 to 60% by mass relative 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: cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative dispersants (dispersion aids). 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, and having 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 the colorant. The amount of the dispersant to be blended is preferably 1 to 35 parts by mass, more preferably 2 to 25 parts by mass, based on the light-shielding component. In addition, high-viscosity substances such as resins generally have an action of stabilizing dispersion, but substances having no dispersion-accelerating ability are not treated as a dispersant. However, the use for the purpose of stabilizing the dispersion is not limited.
As the fine particles as component (E), alumina, silica, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, strontium carbonate, sodium metasilicate, and the like can be used. Among these, fine particles of alumina are preferable. Since the refractive index of a transparent substrate such as glass is about 1.5, and the refractive index of carbon black as a light-shielding component is about 2.0, the refractive index of a cured film containing fine particles can be reduced by using fine particles having a refractive index lower than that of the light-shielding component. The refractive index of the fine particles as component (E) is preferably 1.50 to 1.80, more preferably 1.55 to 1.75. Since the alumina fine particles have a refractive index of 1.74 (literature value) and a refractive index in the vicinity of the middle between the transparent substrate and the light-shielding component, it is considered that the difference in refractive index between the glass and the cured film is small and the reflectance is reduced by using the fine particles. In addition, particles having a large refractive index such as the component (E) are often large in specific gravity, and tend to be biased to exist in the vicinity of the interface between the transparent base material and the cured film when the photosensitive resin composition is applied to a substrate. Therefore, even if the amount of the component (E) is small, the difference in refractive index between the substrate and the cured film can be sufficiently reduced, and reflection can be suppressed. Further, by making the component (E) small, the relative content of the component (D) can be increased, and the optical density of the cured film can be increased. It is considered that the component (E) can achieve both high light-shielding properties and low reflectance of the cured film by the action thereof. Further, by reducing the amount of the component (E), burrs at the edge portions of the pattern due to the component (E) are less likely to be generated.
The alumina particles used in the present invention 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).
(E) The average particle diameter of the component (A) is preferably 10 to 300nm, more preferably 50 to 250nm, still more preferably 55 to 250nm. When the average particle diameter of the particles is 10nm or more, the particle diameter is sufficiently large, and the particles are heavy and tend to be unevenly present in the vicinity of the interface between the transparent base material and the cured film, so that the reflectance reduction effect is easily sufficiently obtained. Further, when the average particle diameter of the particles is 300nm or less, burrs are less likely to be generated at the edges of the pattern. The average particle diameter is an average primary particle diameter when the component (E) contains primary particles, and is an average primary particle diameter when the component (E) contains secondary particles.
The blending ratio of the component (E) is preferably 1 to 30% by mass, more preferably 2 to 10% by mass, based on the solid content in the photosensitive resin composition. When the content of the component (E) is 1 mass% or more, the refractive index of the cured film is sufficiently increased, and the reflectance reducing effect is improved. When the content of the component (E) is 30% by mass or less, a high-definition pattern can be formed.
(D) The blending ratio of the component (E) to the component (D) is preferably 85/15 to 99/1, more preferably 92/8 to 98/2 in terms of the weight ratio (D)/(E). The light-shielding property of the cured film can be further improved by setting the blending ratio of the component (D) to the component (E) to 85/15 or more. In addition, by reducing the relative amount of the (E) component, burrs at the edge portions of the pattern due to the (E) component can be made less likely to occur. Even if the relative amount of the component (E) is reduced to the above-mentioned extent, the effect of reducing the reflectance by the component (E) can be sufficiently exhibited.
In the photosensitive resin composition of the present invention, it is preferable to use a solvent as the component (F) in addition to the components (a) to (E). 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 fine particles having a refractive index of 1.50 to 1.80, 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 fillers include: glass fibers, silica, mica, 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 80 mass% or more of an unsaturated group-containing photosensitive resin as the component (a), a photopolymerizable compound 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), and (E) fine particles having a refractive index of 1.50 or more and 1.80 or less, more preferably 90 mass% or more, in total, in a solid component excluding a solvent (the solid component includes the photopolymerizable compound which becomes the solid component after curing). 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 cured film obtained by curing the photosensitive resin composition of the present invention can be obtained, for example, as follows: a solution of the photosensitive resin composition is applied to a substrate or the like, dried with a solvent, and 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.
In addition, regarding the cured film obtained by curing the photosensitive resin composition of the present invention, the light-shielding degree OD [ μm ] of the cured film having a film thickness of 1 μm -1 ]Preferably 2.6 or more, more preferably 3.0 or more, and still more preferably 3.3 or more. The reflectance of the cured film obtained by curing the photosensitive resin composition of the present invention is preferably 6.5% or less, and more preferably 5.0% or less. The reflectance [% of the cured film obtained by curing the photosensitive resin composition of the present invention]Divided by the shade OD [ mu ] m -1 ]The value obtained is preferably less than 1.65, more preferably less than 1.50. Light-shielding degree OD [ mu ] m of a cured film having a film thickness of 1 mu m -1 ]In the higher light-shielding region, the reflectance is suppressed, and thus a display device having a cured film (light-shielding film) extremely excellent in visibility as a black matrix can be obtained.
In particular, the cured film obtained by curing the photosensitive resin composition of the present invention can be used in the following ranges: light-shielding degree OD [ mu ] m of cured film having film thickness of 1 mu m -1 ]Is 2.6 or more and [% by reflectance%]The value obtained by dividing the thickness by the light-shielding degree OD is less than 1.65, the reflectance is 6.5% or less, and the light-shielding degree OD [ mu ] m of the cured film with the film thickness of 1 mu m is preferred -1 ]Is 3.0 or more and is measured in reflectance [%]The value obtained by dividing the thickness by the light-shielding degree OD is less than 1.50, and the reflectance is 5.0% or less, more preferably the light-shielding degree OD [ mu ] m of a cured film having a film thickness of 1 mu m -1 ]Is 3.3 or more and [% by reflectance%]The value obtained by dividing the light shielding degree OD is less than 1.50, and the reflectance is in the range of 5.0% or less.
The color filter or touch panel having the cured film (light-shielding film) of the present invention as a black matrix can be produced, for example, by: forming a cured film having a thickness of 1.0 to 2.0 μm on a transparent substrate, and forming red, blue and green pixels by photolithography after forming a light-shielding film; in addition, red, blue, and green inks are injected into the light-shielding film by an ink-jet process.
The cured film obtained by curing the photosensitive resin composition of the present invention can also 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 the portions functioning as a spacer and the other portion functioning as a black matrix.
The respective steps of the method for forming a cured 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 solvent is removed (prebaked), thereby forming a coating film. 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 450nm. 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 by using a commercially available developing machine, ultrasonic cleaner, or the like. Further, after the alkali development, water washing is generally performed. As the developing method, a shower developing method, a spray developing method, a dip (dip) developing method, a liquid immersion (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 hard film (light-shielding film) and the substrate. This can be performed by heating in an oven, a hot plate, or the like, as in the case of the prebaking. The patterned hard coat film (light-shielding film) of the present invention is formed through each step by photolithography. Further, polymerization or curing (both may be collectively referred to as curing) is completed by heat, whereby a light-shielding film having a desired pattern can be obtained. The curing temperature in this case is preferably 160 to 250 ℃.
As described above, the photosensitive resin composition 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 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 a liquid crystal projector, a touch panel, and the like. The photosensitive resin composition 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 organic Electroluminescence (EL) devices, color liquid crystal display devices, color facsimiles, and image sensors, in addition to color filter inks for color liquid crystal displays. 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 emitted 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.
First, a description will be given of synthetic examples of the alkali-soluble resin containing a polymerizable 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 weighing [ W1 (g) ] and determining the weight [ W2 (g) ] from the weight [ W2 (g) ] of the resultant mixture after heating at 160 ℃ for 2 hours according to the following formula.
Solid content concentration (% by weight) =100 × (W2-W0)/(W1-W0)
[ acid value ]
The resin solution was dissolved in dioxane and titrated with a 1/10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Pongan industries, ltd.).
[ molecular weight ]
The weight average molecular weight (Mw) was determined by using a Gel Permeation Chromatograph (GPC) "HLC-8220GPC" (manufactured by Tosoh, inc.), tetrahydrofuran as a solvent, and TSKgelsuper H-2000 (2 columns) + TSKgelsuper H-3000 (1 column) + TSKgelsuper H-4000 (1 column) + TSKgelsuper H-5000 (1 column) (manufactured by Tosoh, inc.), a temperature of 40 ℃ and a speed of 0.6ml/min as conversion values of standard polystyrene (manufactured by Tosoh, inc., PS-oligomer).
[ average particle diameter ]
The average particle diameter of the alumina particles was determined by an accumulation method using a particle size distribution analyzer "particle diameter Analyzer FPAR-1000" (manufactured by Otsuka electronics Co., ltd.) using a dynamic light scattering method.
Abbreviations used in synthesis examples and the like are as follows.
BPFE: reaction products of 9, 9-bis (4-hydroxyphenyl) fluorene with chloromethyl oxetane. In the compound of the general formula (1), X is fluorene-9, 9-diyl, R 1 ～R 4 Hydrogen and an epoxy compound with l of 0 to 0.15.
DCPMA: dicyclopentyl methacrylate (dicyclopentanyl methacrylate)
GMA: glycidyl methacrylate (glycidyl methacrylate)
St: styrene (styrene)
AA: acrylic acid (acrylic acid)
BPDA:3,3', 4' -biphenyltetracarboxylic dianhydride (3, 3', 4' -biphenyl tetracarboxylic dianhydride)
THPA: tetrahydrophthalic anhydride (tetrahydrophthalic anhydride)
And SA: succinic anhydride (succinic anhydride)
TEAB: tetraethylammonium bromide (tetra ethyl ammonium bromide)
AIBN: azobisisobutyronitrile (azobisibutyronitrile)
TDMAMP: tris-dimethylaminomethylphenol (tris-dimethyl amino methyl phenol)
HQ: hydroquinone (hydroquinone)
TEA: triethylamine (triethylamine)
TPGDA: tripropylene glycol diacrylate (tripropylene glycol diacrylate)
PGMEA: propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether acetate)
[ Synthesis example A1]
BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g) and TEAB (0.48 g) 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 effect a reaction. Then, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were put into the flask and stirred at 120 ℃ to 125 ℃ for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin (A) -1. The resin solution thus obtained had a solid content of 56.1% by mass, an acid value (in terms of solid content) of 103mgKOH/g, and Mw of 3600 by GPC analysis.
[ Synthesis example A2]
A1L four-necked flask equipped with a reflux condenser was charged with PGMEA (300 g), and the inside of the flask system was purged with nitrogen, followed by heating to 120 ℃. Subsequently, a mixture in which the monomer mixture (DCPMA (77.1 g, 0.35 mol)), GMA (49.8 g, 0.35 mol), st (31.2 g, 0.30 mol)) and AIBN (10 g) were dissolved was added dropwise from a dropping funnel over 2 hours, and further stirred at 120 ℃ for 2 hours to obtain a copolymer solution.
Subsequently, after the flask was purged with air, AA (24.0 g, 0.33 mol (95% of the molar number of GMA added) TDMAMP (0.8 g) and HQ (0.15 g) were added to the obtained copolymer solution, and the mixture was stirred at 120 ℃ for 6 hours to obtain a copolymer solution containing a polymerizable unsaturated group. SA (30.0 g, 90% of the molar amount of AA added) and TEA (0.5 g) were added to the obtained copolymer solution containing a polymerizable unsaturated group, and the mixture was reacted at 120 ℃ for 4 hours to obtain an alkali-soluble resin (A) -2 containing an unsaturated group. The resin solution had a solid content of 46.0% by mass, an acid value (in terms of solid content) of 76mgKOH/g, and Mw, as determined by GPC analysis, of 5300.
Further, carbon black having a surface coated with a dye was prepared by the following method.
[ preparation example D1]
1000g of carbon black (TPX-1099, manufactured by Cabot corporation) was mixed with water to prepare 10L of slurry, which was stirred at 95 ℃ for 1 hour, left to cool, and then washed with water. This was mixed with water again to prepare 10L of a slurry, and 42.9g of 70% nitric acid was added thereto and stirred at 40 ℃ for 4 hours. After the mixture was left to cool and washed with water, it was mixed with water again to prepare 10L of slurry, and 13% aqueous sodium hypochlorite solution 769.2g was added thereto and stirred at 40 ℃ for 6 hours. The mixture was left to cool, washed with water, and mixed with water again to prepare 10L of slurry, 38.1g of a dye (Direct Deep Black) having a purity of 38.4% was added thereto, and the mixture was stirred at 40 ℃ for 1 hour, then 10.1g of aluminum sulfate was further added thereto, and the mixture was stirred at 40 ℃ for 1 hour. After leaving to cool, the mixture was washed with water and filtered and dried to obtain dye-coated carbon black.
The dye-coated carbon black, the polymer dispersant, the dispersion resin (alkali-soluble resin ((a) -1) of synthesis example A1), and PGMEA were mixed and dispersed by a bead mill to obtain a carbon black dispersion (D) -1 having a concentration of the dye-coated carbon black of 25.0 mass%, a concentration of the polymer dispersant of 2.0 mass%, and a concentration of the dispersion resin of 8.0 mass%.
Photosensitive resin compositions of examples 1 to 7 and comparative examples 1 to 3 were prepared in the blending amounts (unit is part by mass) shown in table 1. The formulation ingredients used in table 1 are as follows.
(alkali-soluble resin containing polymerizable unsaturated group)
(A) -1: the alkali-soluble resin solution (solid content concentration: 56.1% by mass) obtained in Synthesis example A1 was used
(A) -2: the alkali-soluble resin solution (solid content concentration: 46.0% by mass) obtained in Synthesis example A2
(photopolymerizable Compound)
(B) The method comprises the following steps Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA (acrylic equivalent 96-115), manufactured by Nippon chemical 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 okls, adeka Act, adeka arkls, inc.' which is a registered trademark of Adeka Act
(carbon Black Dispersion liquid)
(D) -1: the pigment dispersion (solid content: 35 mass%) of the PGMEA solvent having a dye-coated carbon black concentration of 25 mass%, a polymer dispersant concentration of 2 mass%, and a dispersion resin (alkali-soluble resin ((a) -1) of synthetic example A1) concentration of 8 mass% obtained in preparation example D1 was prepared
(D) -2: a pigment dispersion (solid content: 33 mass%) of a PGMEA solvent having a carbon black concentration of 25 mass%, a polymeric dispersant concentration of 3 mass%, and a dispersion resin (alkali-soluble resin ((A) -1) of Synthesis example A1) concentration of 5 mass%
(E) -1: an alumina TPGDA dispersion "ALTPGDA 30WT% -A03" (manufactured by CIK nanotechnology Co., ltd., alumina concentration 30 mass%, TPGDA concentration 70 mass%, average particle diameter 90 nm)
(E) -2: an alumina TPGDA dispersion "ALTPGDA 25WT% -A07" (manufactured by CIK nanotechnology Co., ltd., alumina concentration 25 mass%, TPGDA concentration 75 mass%, average particle diameter 50 nm)
(E) -3: the silica PGMEA dispersion "YA050C" (manufactured by Admacech technologies, inc., 30 mass% silica concentration, 70 mass% PGMEA concentration, and 50nm average particle diameter)
(solvent)
(F) -1: propylene Glycol Monomethyl Ether Acetate (PGMEA)
(F) -2: cyclohexanone (ANON)
(other ingredients) -1: 3-isocyanatopropyltriethoxysilane (KBE-9007N, from shin-Etsu chemical Co., ltd.)
(other Components) -2: diluted 1% by mass ANON solution of aralkyl-modified polymethylalkylsiloxane (BYK-323, manufactured by Nippon chemical Co., ltd.)
Figure BDA0003868620990000231
[ evaluation ]
A cured film (light-shielding film) obtained by curing the photosensitive resin composition for evaluation was produced as follows.
(preparation of cured film (coating film) for Optical Density (OD) evaluation)
Using a spin coater, the photosensitive resin compositions shown in Table 1 were applied to a film previously irradiated with a low-pressure mercury lamp at a wavelength of 254nm and an illuminance of 1000mJ/cm so that the film thickness after heat curing treatment became 1.2. Mu.m 2 The surface of a 125mm × 125mm glass substrate "#1737" (manufactured by corning) (hereinafter referred to as "glass substrate") was cleaned with ultraviolet rays, and pre-baked at 90 ℃ for 1 minute using a hot plate to form a cured film (coating film). Using an i-ray with an illuminance of 30mW/cm without coating a negative photomask 2 Is irradiated by an extra-high pressure mercury lamp at 50mJ/cm 2 The ultraviolet ray of (2) to perform a photo-curing reaction.
Then, the cured film after exposure is subjected to light shieldingFilm) at 25 ℃ with a 0.05% potassium hydroxide solution at 1kgf/cm 2 The development treatment was carried out for 20 seconds from the development time (break time) = BT) at which the pattern began to appear, and then 5kgf/cm was carried out 2 The unexposed portion of the cured film (light-shielding film) was removed to form a cured film pattern on the glass substrate, and the cured film (light-shielding film) of examples 1 to 7 and comparative examples 1 to 3 was obtained by main curing (post-baking) at 230 ℃ for 30 minutes using a hot air dryer.
[ measurement of film thickness ]
(evaluation method)
The level difference between the surface of the glass substrate and the surface of the cured film was measured using a level difference meter ("croday (Tencor) P-17" manufactured by KLA-Tencor) under the conditions of a measurement range of 500 μm, a scanning speed of 50 μm/sec, and a sampling rate of 20Hz, and the average value thereof was defined as the average thickness of the cured film.
[ evaluation of Optical Density (OD) ]
(evaluation method)
The Optical Density (OD) was measured using a transmission densitometer ("Alice (X-rite) 361T (V)" manufactured by Alice (X-rite) Co., ltd.). The Optical Density (OD) per 1 μm film thickness was calculated from the measured film thickness and Optical Density (OD).
The Optical Density (OD) is calculated by the following formula (5).
Optical Density (OD) = -log 10 T type (5)
(T represents a transmittance)
[ evaluation of reflectance ]
(evaluation method)
For a substrate with a cured film (light-shielding film) prepared in the same manner as the cured film (light-shielding film) for Optical Density (OD) evaluation, the reflectance of each of the cured film (light-shielding film) side and the substrate (glass substrate) side was measured under the conditions of a C light source, an incident angle of 2 °, and a wavelength range of 380nm to 780nm using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science).
(preparation of a cured film (light-shielding film) for evaluation of development Properties)
Using a spin coater, the photosensitive resin compositions shown in Table 1 were applied to a film previously irradiated with a low-pressure mercury lamp at a wavelength of 254nm and an illuminance of 1000mJ/cm so that the film thickness after heat curing treatment became 1.2. Mu.m 2 The surface of a 125mm × 125mm glass substrate "#1737" (manufactured by corning) (hereinafter referred to as "glass substrate") was cleaned with ultraviolet rays, and pre-baked at 90 ℃ for 1 minute using a hot plate to form a cured film (light-shielding film). Subsequently, the exposure gap was adjusted to 100 μm, and the dry cured film was covered with a negative photomask having a line/space =10 μm/50 μm, and i-ray was used with an illuminance of 30mW/cm 2 Is irradiated by an extra-high pressure mercury lamp at 50mJ/cm 2 The ultraviolet ray of (2) to perform a photo-curing reaction of the photosensitive portion.
Then, the hardened film (light-shielding film) after exposure was treated with a 0.04% potassium hydroxide solution at 25 ℃ in a range of 1kgf/cm 2 The shower pressure of (2) was subjected to a development treatment for +20 seconds from a development time (break time) = BT) at which the pattern began to appear, and then to 5kgf/cm 2 The unexposed portion of the cured film (light-shielding film) was removed to form a cured film pattern on the glass substrate, and the cured film (light-shielding film) of examples 1 to 7 and comparative examples 1 to 3 was obtained by main curing (post-baking) at 230 ℃ for 30 minutes using a hot air dryer.
The cured films (light-shielding films) obtained by curing the photosensitive resin compositions of examples 1 to 7 and comparative examples 1 to 3 were evaluated for the following items.
[ evaluation of development Properties ]
(straightness of Pattern)
(evaluation method)
The 10 μm mask pattern for the positive hardening (post-baking) was observed using an optical microscope. Further, the evaluation of the pattern linearity was performed in the case of BT +20 seconds. In addition, Δ or more is defined as pass.
(evaluation criteria for development Properties)
O: when the pattern length was set to 100%, only projections of 0.5 μm, less than 1%, were observed in the burrs at the edge of the pattern with respect to the line width of 10 μm
And (delta): when the length of the pattern is 100%, the burr at the edge of the pattern is observed to be more than 1% and less than 25% of 0.5 μm protrusion relative to the line width of 10 μm
X: when the length of the pattern is 100%, the burr at the edge of the pattern is observed to be 0.5 μm protrusion with a ratio of 25% or more relative to the line width of 10 μm
The evaluation results are shown in table 2.
[ Table 2]
Figure BDA0003868620990000261
In the photosensitive resin compositions of examples 1 to 7, it was confirmed that the refractive index was high and the reflectance from the substrate side was reduced as compared with the systems using silica particles (comparative examples 1 to 3). In addition, it was confirmed that the cured films (light-shielding films) obtained by curing the photosensitive resin compositions of examples 1 to 3 and 5 had good pattern linearity.
[ industrial applicability ]
The photosensitive resin composition of the present invention can provide a photosensitive resin composition having both high light-shielding properties and low reflectance, and a cured film, a color filter, and a touch panel using the same. In addition, various display devices having excellent visibility can be provided by the color filter and the touch panel.

Claims (9)

1. A photosensitive resin composition comprising:
(A) An alkali-soluble resin containing an unsaturated group;
(B) A photopolymerizable compound 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, mixed color pigments, and light-shielding materials; and
(E) Fine particles having a refractive index of 1.50 to 1.80.
2. The photosensitive resin composition according to claim 1, wherein the fine particles (E) are alumina particles.
3. The photosensitive resin composition according to claim 1 or 2, wherein the fine particles (E) have an average particle diameter of 10nm to 300nm.
4. The photosensitive resin composition according to claim 1 or 2, wherein the proportion of the fine particles (E) in the solid content is 1 to 30% by mass.
5. The photosensitive resin composition according to claim 1 or 2, wherein a cured film having a film thickness of 1 μm obtained by curing the photosensitive resin composition by light has a light-shielding optical density of 2.6 μm -1 The cured film has a reflectance of 6.5% or less, and the reflectance of the cured film divided by the light-shielding optical density is less than 1.65.
6. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 5.
7. A color filter having the cured film according to claim 6 as a black matrix.
8. A touch panel having the hardened film according to claim 6 as a black matrix.
9. A display device having the color filter according to claim 7 or the touch panel according to claim 8.
CN202211189465.7A 2021-09-30 2022-09-28 Photosensitive resin composition, cured film, color filter, touch panel, and display device Pending CN115903385A (en)

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