CN113467186A - Photosensitive resin composition, cured film thereof, and color filter having the cured film - Google Patents

Photosensitive resin composition, cured film thereof, and color filter having the cured film Download PDF

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Publication number
CN113467186A
CN113467186A CN202110338904.5A CN202110338904A CN113467186A CN 113467186 A CN113467186 A CN 113467186A CN 202110338904 A CN202110338904 A CN 202110338904A CN 113467186 A CN113467186 A CN 113467186A
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acid
group
meth
general formula
resin composition
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滑川崇平
高野正臣
内田一幸
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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
    • 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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/02—Homopolymers or copolymers of esters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Optical Filters (AREA)

Abstract

The invention relates to a photosensitive resin composition, a cured film thereof and a color filter with the cured film. The present invention relates to a photosensitive resin composition and a cured film thereof, which can reduce the reflectivity by a simple method, and can form a high-definition pattern with high light-shielding performance. The invention provides a photosensitive resin composition, which comprises the following resin components: an alkali-soluble resin (i) containing a polymerizable unsaturated group, which is obtained by reacting a reactant of an epoxy compound having 2 or more phenylglycidyl ether groups in the molecule and a monocarboxylic acid containing an unsaturated group, with a dicarboxylic acid or a tricarboxylic acid or an acid monoanhydride thereof, and a tetracarboxylic acid or an acid dianhydride thereof, and has a weight-average molecular weight of 2500 or more; and (meth) acrylate resin (ii) having a weight average molecular weight of 6000 or more, the weight average molecular weight having a carboxyl group and a polymerizable unsaturated group in a side chain; and the photosensitive resin composition contains a light-shielding material (iii) selected from the group consisting of a black organic pigment, a black inorganic pigment or a mixed color organic pigment as an essential component.

Description

Photosensitive resin composition, cured film thereof, and color filter having the cured film
Technical Field
The invention relates to a photosensitive resin composition, a cured film thereof and a color filter with the cured film.
Background
In general, flat panel displays such as liquid crystal displays are provided with an antireflection layer in order to reduce reflection of light incident from the outside. Anti-reflection layers include Anti-glare (AG) films and Anti-reflection (AR) films (Anti-reflection films). The AG film is formed with irregularities on the surface of the hard coat resin layer to scatter reflected light, and further prevents reflection glare by internal scattering due to the difference in refractive index between the hard coat resin and the particles. However, the contrast is reduced by scattering of reflected light from the surface, and the resolution is reduced by internal scattering of transmitted light from the backlight. On the other hand, the AR film is mainly formed by alternately laminating 2 types of layers having different refractive indices, and can reduce reflected light by interference of light. Further, recently, there is also a moth-eye method in which fine unevenness having a refractive index that continuously changes is formed on the surface of the AR film by nanoimprinting or the like. The AR film suppresses contrast reduction due to scattered light on the surface or resolution reduction due to internal scattering, and is the mainstream of the antireflection layer.
In recent years, with the miniaturization and high resolution of displays, higher contrast and higher definition have been required, and antireflection layers also have been required to have reduced reflectance and improved surface smoothness. In particular, since the visibility is greatly affected when the antireflection layer is set to be used for an outdoor portable information terminal, a digital signage, a car display, or the like, the antireflection layer is required to have high characteristics. The improvement of the anti-reflection layer can greatly improve the visibility of the display, but the reduction of the reflectivity of each component except the anti-reflection layer is also required.
The components other than the antireflection layer may be, for example, color filters used in liquid crystal displays. The color filter includes a coloring material constituting a pixel, a black matrix for dividing the pixel, a protective film for protecting the pixel, and the like. In particular, the coloring material used for the black matrix is often high in refractive index, and has a large influence on the reflectance of the color filter. As a method of reducing the reflectance of the black matrix, although the amount of the coloring material is reduced, the light-shielding property is reduced, and the contrast of the image is easily reduced.
In addition, as a self-luminous type display that does not use a color filter, an organic electroluminescence display has been sold, and in recent years, a display using a micro LED or a quantum dot for a pixel has also been developed. These self-luminous displays generally do not use color filters, but if the reflectivity of the rear wall of the divided pixel seven is high, the visibility is easily reduced.
Patent document 1, patent document 2, and patent document 3 disclose black matrices in which 2 layers (a light-shielding higher layer on a light-shielding lower layer) having different optical densities are stacked.
Patent document 4 discloses a colored cured film having a low reflectance on the opposite side of the substrate (reflectance on the surface side of the colored cured film).
[ Prior art documents ]
[ patent document ]
Patent document 1: japanese patent laid-open publication No. 2014-157179
Patent document 2: japanese patent laid-open No. 2014-130368
Patent document 3: international publication No. 2014/136738
Patent document 4: japanese patent laid-open publication No. 2018-141849.
Disclosure of Invention
[ problems to be solved by the invention ]
The present inventors have found that the methods disclosed in patent documents 1, 2, and 3 are expected to improve visibility because the refractive index of the black matrix is low with respect to light entering from the substrate side on which the color filter is formed. However, after the low light-shielding layer is formed on the substrate, the manufacturing process of the color filter may become complicated to stack the high light-shielding layer, and productivity may be reduced.
In addition, in the colored cured film disclosed in patent document 4, since the silica particles are present on the surface of the colored cured film, unevenness may be generated on the surface of the colored cured film. Therefore, instead of reducing specular reflection by surface irregularities, diffuse reflection may be increased, and whitening or dullness may occur due to the increase in diffuse reflection, resulting in a reduction in texture.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a photosensitive resin composition which can reduce reflectance by a simple method and can achieve both high light-shielding properties and formation of a high-definition pattern, a cured film thereof, and a color filter having the cured film.
[ means for solving the problems ]
The present inventors have made extensive studies to solve the above problems, and as a result, have found that a photosensitive resin composition which can reduce reflectance by a simple method and can achieve both high light-shielding properties and high-definition pattern formation can be obtained by using 2 types of resins having specific structures.
That is, the photosensitive resin composition of the present invention contains, as resin components: an alkali-soluble resin (i) containing a polymerizable unsaturated group, which is obtained by reacting a reactant of an epoxy compound having 2 or more phenylglycidyl ether groups in the molecule and a monocarboxylic acid containing an unsaturated group, with a dicarboxylic acid or a tricarboxylic acid or an acid monoanhydride thereof, and a tetracarboxylic acid or an acid dianhydride thereof, and has a weight-average molecular weight of 2500 or more; and (meth) acrylate resin (ii) having a weight average molecular weight of 6000 or more and having a carboxyl group and a polymerizable unsaturated group in a side chain, wherein the photosensitive resin composition contains a light shielding material (iii) selected from the group consisting of a black organic pigment, a black inorganic pigment, and a mixed color organic pigment as an essential component.
The cured film of the present invention is obtained by curing the photosensitive resin composition.
In addition, the color filter of the present invention has the cured film as a black matrix.
[ efficacy of the invention ]
The invention provides a photosensitive resin composition which can reduce the reflectivity by a simple method and can combine high light-shielding performance and form high-fine patterns, a cured film thereof and a color filter with the cured film.
Detailed Description
The following describes embodiments of the present invention, but the present invention is not limited to the following embodiments. In the present invention, when the content of each component is 0 in the first place after decimal point, the marks after decimal point are omitted.
The photosensitive resin composition according to one embodiment of the present invention contains, as resin components: an alkali-soluble resin (i) containing a polymerizable unsaturated group, which is obtained by reacting a reactant of an epoxy compound having 2 or more phenylglycidyl ether groups in the molecule and a monocarboxylic acid containing an unsaturated group, with a dicarboxylic acid or a tricarboxylic acid or an acid monoanhydride thereof, and a tetracarboxylic acid or an acid dianhydride thereof, and which has a weight average molecular weight of 2500 or more; and (meth) acrylate resin (ii) having a weight average molecular weight of 6000 or more, the weight average molecular weight having a carboxyl group and a polymerizable unsaturated group in a side chain; and the photosensitive resin composition contains a light shielding material (iii) selected from the group consisting of a black organic pigment, a black inorganic pigment or a mixed color organic pigment as an essential component.
The components (i) to (iii) are described below.
(alkali-soluble resin containing polymerizable unsaturated group)
The alkali-soluble resin containing a polymerizable unsaturated group, component (i) of one embodiment of the present invention has a weight average molecular weight of 2500 or more, as represented by the following general formula (1).
Figure BDA0002998701700000041
(in the formula (1), R1Independently a hydrocarbon group of carbon number 2 to 4, R2Independently a hydrocarbon group of carbon number 1 to 3, R3Independently a hydrogen atom or a methyl group, X independently is a C1-20 organic group having a valence of 2, -CO-, -SO2-、-C(CF3)2-、-CH2-、-C(CH3)2-、-Si(CH3)2-, -O-, a fluorene-9, 9-diyl group represented by the general formula (2) or a single bond, Y is a 4-valent carboxylic acid residue, Z is independently a hydrogen atom or a substituent represented by the general formula (3), but at least 1 of Z is a substituent represented by the general formula (3), G is independently a hydrogen atom or a substituent represented by the general formula (4), a is independently a number of 0 to 10, an average value of a in 1 molecule is also a number of 0 to 10, and an average value of a in the composition is also a number of 0 to 10. b is independently a number from 0 to 4, the average value of b in 1 molecule is also a number from 0 to 4, and the average value of b in the composition is also a number from 0 to 4. n is an integer having an average value of 1 to 20. )
Figure BDA0002998701700000042
(in the formulae (3) and (4), R4、R6Is a hydrogen atom or a methyl group, R5、R7Is a hydrocarbon group having 2 to 4 carbon atoms, L is a 2-or 3-valent carboxylic acid residue, c and f are numbers of 0 or 1, d and e are numbers of 0, 1 or 2, and d + e is a number of 1 or 2. )
A method for producing the polymerizable unsaturated group-containing alkali-soluble resin (i) having a weight average molecular weight of 2500 or more represented by the above general formula (1) (hereinafter referred to as "alkali-soluble resin represented by the general formula (1)") will be described.
First, a bisphenol-type epoxy compound (a-1) having 2 or more phenylglycidyl ether groups in 1 molecule represented by the following general formula (8) (hereinafter referred to as "epoxy compound represented by the general formula (8)") is reacted with an unsaturated group-containing monocarboxylic acid (e.g., (meth) acrylic acid) to obtain a diol having a polymerizable unsaturated group. In addition, "(meth) acrylic acid" is a generic name of acrylic acid and methacrylic acid, and indicates one or both of these.
Figure BDA0002998701700000051
(in the formula (8), R1Independently a hydrocarbon group of carbon number 2 to 4, R2Independently a hydrocarbon group having 1 to 3 carbon atoms, X independently is a C1-20 2-valent organic group, -CO-, -SO2-、-C(CF3)2-、-CH2-、-C(CH3)2-、-Si(CH3)2-, -O-, a fluorene-9, 9-diyl group represented by the general formula (2) or a single bond, a is independently a number of 0 to 10, and b is independently a number of 0 to 4. )
Figure BDA0002998701700000052
The epoxy compound represented by the general formula (8) is an epoxy compound having 2 phenylglycidyl ether groups in 1 molecule obtained by reacting a bisphenol with epichlorohydrin. This reaction generally involves oligomerization of a diglycidyl ether compound, and therefore contains an epoxy compound having 2 or more bisphenol skeletons.
Examples of the above bisphenols 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.
Examples of the monocarboxylic acid having an unsaturated group which is reacted with the epoxy compound represented by the general formula (8) include acrylic acid and methacrylic acid, and also include compounds obtained by reacting acrylic acid or methacrylic acid with an acid monoanhydride such as succinic anhydride, maleic anhydride or phthalic anhydride.
The reaction of the epoxy compound represented by the general formula (8) with the unsaturated group-containing monocarboxylic acid can be carried out by a known method. For example, Japanese patent application laid-open No. 4-355450 discloses: about 2 moles of (meth) acrylic acid are used per 1 mole of the epoxy compound having 2 epoxy groups, whereby a diol having a polymerizable unsaturated group is obtained. In the present invention, the reactant obtained by the above reaction is a diol (d) containing a polymerizable unsaturated group represented by general formula (9) (hereinafter referred to as "diol represented by general formula (9)").
Figure BDA0002998701700000061
(in the formula (9), R1Independently a hydrocarbon group of carbon number 2 to 4, R2Independently a hydrocarbon group of carbon number 1 to 3, R3Independently a hydrogen atom or a methyl group, X independently is a C1-20 organic group having a valence of 2, -CO-, -SO2-、-C(CF3)2-、-CH2-、-C(CH3)2-、-Si(CH3)2-, -O-, a fluorene-9, 9-diyl group represented by the general formula (2) or a single bond, a is independently a number of 0 to 10, and b is independently a number of 0 to 4. )
Figure BDA0002998701700000071
Examples of the above-mentioned 2-valent organic group having 1 to 20 carbon atoms include a 2-valent hydrocarbon group, a 2-valent group having one or two carboxyl groups in a side chain of the hydrocarbon group, and the like. The hydrocarbon group may have an oxygen atom or an ester bond having an ether bond therein.
In addition, examples of the above-mentioned 2-valent hydrocarbon group include: and linear or branched hydrocarbon groups such as methylene, vinyl, propylene, isopropylene, secondary butylene, methylisobutylene, hexylene, decylene, and dodecylene groups. Examples of the 2-valent group having an ester bond in the hydrocarbon group include 2-valent organic groups represented by general formulae (10) to (12).
Figure BDA0002998701700000072
(in the formula (10), h is an integer of 1 to 20.)
Figure BDA0002998701700000073
(in the formula (11), i is an integer of 2 to 20, and j is an integer of 0 to 10.)
Figure BDA0002998701700000074
(in the formula (12), k is an integer of 0 to 18, and l is independently an integer of 1 to 10.)
Examples of the (a) dicarboxylic acid or tricarboxylic acid or acid monoanhydride thereof which reacts with the hydroxyl group in the diol molecule represented by the general formula (9) of the reactant of the epoxy compound represented by the general formula (8) and monocarboxylic acid having an unsaturated group include chain type hydrocarbon dicarboxylic acid or tricarboxylic acid or acid monoanhydride thereof, alicyclic dicarboxylic acid or tricarboxylic acid or acid monoanhydride thereof, aromatic dicarboxylic acid or tricarboxylic acid or acid monoanhydride thereof, and the like.
Examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or the acid monoanhydride thereof include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid (citramalic acid), malonic acid, glutaric acid, citric acid, tartaric acid, lateral oxygen glutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like. Further, dicarboxylic acids and tricarboxylic acids having any of these substituents introduced therein, and acid monoanhydrides thereof are also included.
Examples of the alicyclic dicarboxylic acid or tricarboxylic acid or the acid monoanhydride thereof include acid monoanhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid and the like. Further, dicarboxylic acids, tricarboxylic acids, or acid monoanhydrides thereof into which any of these substituents is introduced are also included.
Examples of the above aromatic dicarboxylic acid or tricarboxylic acid or the acid monoanhydride of these include phthalic acid, isophthalic acid, trimellitic acid, and the acid monoanhydride of these. Further, dicarboxylic acids or tricarboxylic acids having any of these substituents introduced therein and the acid monoanhydrides thereof are also included.
Among the dicarboxylic acids, tricarboxylic acids, or their monoanhydrides, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are more preferable, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferable. Further, among the above-mentioned dicarboxylic acids and tricarboxylic acids, the use of acid monoanhydrides thereof is more preferable. The acid monoanhydrides of the above-mentioned dicarboxylic acids or tricarboxylic acids may be used alone in 1 kind or in combination with 2 or more kinds.
Examples of the tetracarboxylic acid or the acid dianhydride thereof (b) which reacts with the hydroxyl group in the diol molecule represented by the general formula (9) which is a reactant of the epoxy compound represented by the general formula (8) and the monocarboxylic acid having an unsaturated group include chain hydrocarbon tetracarboxylic acids, alicyclic hydrocarbon tetracarboxylic acids, aromatic hydrocarbon tetracarboxylic acids, and acid dianhydrides thereof.
Examples of the chain hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids having an alicyclic hydrocarbon group, an unsaturated hydrocarbon group, or other substituent introduced therein.
Examples of the alicyclic tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornane-tetracarboxylic acid, and alicyclic tetracarboxylic acids having a substituent such as a chain hydrocarbon group or an unsaturated hydrocarbon group introduced therein.
Examples of the aromatic tetracarboxylic acid include pyromelic acid, diphenylketotetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid and the like.
Among the tetracarboxylic acids, biphenyltetracarboxylic acid, diphenylketotetracarboxylic acid and diphenylethertetracarboxylic acid are more preferable, and biphenyltetracarboxylic acid and diphenylethertetracarboxylic acid are still more preferable. In addition, the tetracarboxylic acid or its acid dianhydride is preferably used. The tetracarboxylic acid or acid dianhydride thereof may be used alone in 1 kind or in combination with 2 or more kinds.
The molar ratio (a)/(b) of the (a) dicarboxylic acid or tricarboxylic acid or acid monoanhydride thereof reacted with the hydroxyl group in the diol molecule represented by the above general formula (9) to the (b) tetracarboxylic acid or acid dianhydride thereof is preferably 0.01 to 10.0, more preferably 0.02 to less than 3.0. When the molar ratio (a)/(b) is 0.01 to 10.0, the most preferable molecular weight for forming a photosensitive resin composition having good photo-patterning properties can be obtained. The smaller the molar ratio (a)/(b), the larger the molecular weight, and the lower the alkali solubility tends to be.
The reaction of the epoxy compound represented by the general formula (8) with the unsaturated group-containing monocarboxylic acid and the reaction of the diol represented by the general formula (9) obtained by the reaction with the polybasic acid or the anhydride thereof are not particularly limited, and a known method can be employed.
The weight average molecular weight (Mw) of the alkali-soluble resin represented by the general formula (1) synthesized by the above reaction is 2500 or more, preferably 2500 or more and 100000 or less, and more preferably 2500 or more and 25000 or less. When the weight average molecular weight (Mw) is 2500 or more, phase separation from the (meth) acrylate resin (described later) results in formation of a thin layer (10 to 100nm) on the outermost layer side (surface not in contact with the substrate) of the cured film, and thus the reflectance can be reduced without providing an antireflection film or the like on the outermost layer side (surface not in contact with the substrate) of the cured film. Further, when 100000 or less, the pattern adhesion can be suppressed from being lowered in the alkali development, and the solution viscosity of the photosensitive resin composition suitable for application can be easily adjusted, so that the alkali development does not take too much time.
The acid value of the alkali-soluble resin represented by the above general formula (1) is preferably 30mg/KOH or more and 200mg/KOH or less, more preferably 40mgKOH/g or more and 140mgKOH/g or less, and still more preferably 80mgKOH/g or more and 120mgKOH/g or less. When the acid value of the alkali-soluble resin is 30mg/KOH or more, a residue is less likely to remain during alkali development. In addition, when the content is 200mgKOH/g or less, the penetration of the alkali developing solution is not too fast, and thus the peeling development can be suppressed.
The weight average molecular weight (Mw) of the alkali-soluble resin represented by the general formula (1) can be measured, for example, by colloid permeation chromatography (GPC) "HLC-8220 GPC" (manufactured by TOSOH GmbH). The acid value of the alkali-soluble resin represented by the general formula (1) can be measured, for example, using a potentiometric titrator "COM-1600" (manufactured by Hei marsh industries, Ltd.).
The alkali-soluble resin represented by the general formula (1) of the component (i) may be used alone in 1 kind or in combination in 2 or more kinds.
The mass of the alkali-soluble resin represented by the general formula (1) is preferably 40 to 99 mass%, more preferably 40 to 90 mass%, and still more preferably 40 to 80 mass% with respect to the total mass of the alkali-soluble resin represented by the general formula (1) and the (meth) acrylate resin represented by the general formula (13) (described later). If the mass of the alkali-soluble resin is 40 to 99 mass%, the reflectance can be reduced while maintaining high-precision pattern formation.
((meth) acrylate resin)
The (meth) acrylate resin having a carboxyl group and a polymerizable unsaturated group in a side chain thereof and a weight average molecular weight of 6000 or more, which is component (ii) in one embodiment of the present invention, is represented by, for example, general formula (13) below. The general formula (13) is a random copolymer having m, o, and p units, respectively.
Figure BDA0002998701700000101
(in the formula (13), R8、R10、R11Independently is a hydrogen atom or a methyl group, R9Is a hydrocarbon group having 1 to 20 carbon atoms, the above-mentioned R9May contain an etheric oxygen atom or a urethane bond inside. R12Independently a 2-valent hydrocarbon group having 2 to 10 carbon atoms, g independently is a number of 0 or 1, and m, o, and p independently are any integer. )
The following describes a method for producing a (meth) acrylate resin (ii) having a carboxyl group and a polymerizable unsaturated group in a side chain thereof and having a weight average molecular weight of 6000 or more (hereinafter referred to as "a (meth) acrylate resin represented by general formula (13)").
The (meth) acrylate resin represented by the general formula (13) according to one embodiment of the present invention is derived from a polyvalent oxycarboxylic compound represented by the following general formula (14) obtained by copolymerizing a (meth) acrylate represented by the general formula (5) with a (meth) acrylic acid represented by the general formula (6). The general formula (14) is a random copolymer having m and o units in each unit.
Figure BDA0002998701700000102
(in the formula (5), R8Is a hydrogen atom or a methyl group, R9Is a hydrocarbon group having 1 to 20 carbon atoms, the above-mentioned R9May contain an etheric oxygen atom or a urethane bond inside. )
Figure BDA0002998701700000111
(in the formula (6), R10Is a hydrogen atom or a methyl group. )
Figure BDA0002998701700000112
(in the formula (14), R8、R10Is a hydrogen atom or a methyl group, R 9Is a hydrocarbon group having 1 to 20 carbon atoms, the above-mentioned R9May contain an etheric oxygen atom or a urethane bond inside. o and m are any integer. )
R represented by the above general formula (5)9Examples of the hydrocarbon group (b) include linear hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, isooctyl, decyl, dodecyl, tetradecyl and eicosyl groups, cyclic aliphatic hydrocarbon groups such as cyclohexyl, norbornyl, isobornyl, tricyclodecylmethyl and decahydronaphthyl groups and substituents represented by the following general formula (15), aliphatic ethers such as methoxyethyl and 2- (methoxyethoxy) ethyl groups, and aliphatic carbamates such as 2- (ethoxycarbonylamino) ethyl group.
Figure BDA0002998701700000113
(in the formula (15), R13Is a hydrogen atom or a methyl group. )
Among the hydrocarbon groups, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, cyclohexyl, norbornyl, isobornyl, and tricyclodecylmethyl groups are more preferable, and methyl, ethyl, cyclohexyl, norbornyl, isobornyl, and tricyclodecylmethyl groups are more preferable.
The (meth) acrylate represented by the above general formula (5) may be used alone in 1 kind or in combination in 2 or more kinds. The (meth) acrylic acid represented by the general formula (6) may be used alone in 1 kind or in combination in 2 or more kinds.
The polycarboxylic acid represented by the general formula (14) is a copolymer in which two components derived from a (meth) acrylate represented by the general formula (5) and a (meth) acrylic acid represented by the general formula (6) are substantially randomly bonded. The copolymerization method is not particularly limited, and a known copolymerization method can be used.
In the polycarboxylic acid represented by the general formula (14), when the repeating unit (m) derived from the constituent component of the (meth) acrylate represented by the general formula (5) and the repeating unit (o) derived from the constituent component of the (meth) acrylic acid represented by the general formula (6) are considered to react with the (meth) acrylate having an epoxy group represented by the general formula (7) and the sum of the numbers of m and o is 100, m is more preferably 20 to 70, and still more preferably 30 to 60. In addition, o is more preferably 30 to 80, and still more preferably 40 to 70. M and o are independently any integer. By setting m to 20 to 70 and o to 30 to 80, both solubility in an alkali developing solution and curability can be achieved.
Next, a part of the carboxyl groups of the polycarboxylic acid compound represented by the general formula (14) is reacted with the (meth) acrylate having an epoxy group represented by the general formula (7), whereby the (meth) acrylate resin represented by the general formula (13) according to one embodiment of the present invention can be obtained. The order of bonding of the constituent components is not particularly limited, and is a copolymer having substantially random bonds.
Figure BDA0002998701700000121
(in the formula (7), R11Is a hydrogen atom or a methyl group, R12Is a 2-valent hydrocarbon group having 2 to 10 carbon atoms, and g is a number of 0 or 1. )
In the general formula (13), the constituent derived from the (meth) acrylate compound represented by the general formula (5), the constituent derived from the (meth) acrylic acid compound represented by the general formula (6), and the constituent derived from the (meth) acrylic acid compound represented by the general formula (6) in which a part of the carboxyl groups of the constituent derived from the (meth) acrylic acid compound is added to the (meth) acrylate having an epoxy group represented by the general formula (7), the bonding order of the 3 constituents is not particularly regular, and the 3 constituents are copolymers in which the 3 constituents are substantially randomly bonded.
When a part of the carboxyl groups in the polycarboxylic acid represented by the general formula (14) is reacted with the (meth) acrylate having an epoxy group represented by the general formula (7), the solvent used is not particularly limited, and a solvent having a boiling point higher than the reaction temperature is more preferable.
Examples of the solvent include a celluloid threo-based solvent such as ethyl celluloid threo-acetate or butyl celluloid threo-acetate, a high-boiling-point ether-based or ester-based solvent such as ethyl carbitol acetate, butyl carbitol acetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, and butyl acetate, and a ketone-based solvent such as cyclohexanone or diisobutyl ketone.
The catalyst to be used is not particularly limited, and examples thereof include tetraethylammonium bromide, ammonium salts such as triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris (2, 6-dimethoxyphenyl) phosphine, as described in Japanese patent application laid-open No. 9-325494.
When the (meth) acrylate resin represented by the general formula (13) is produced by reacting the polycarboxylic acid represented by the general formula (14) with the (meth) acrylate having an epoxy group represented by the general formula (7), the reaction temperature is preferably 20 to 140 ℃, more preferably 40 to 130 ℃.
In addition, when the (meth) acrylate resin represented by the general formula (13) is produced, the addition ratio of the (meth) acrylate having an epoxy group represented by the general formula (7) to the polycarboxylic acid represented by the general formula (14) may be arbitrarily changed for the purpose of adjusting the acid value and curability of the (meth) acrylate resin represented by the general formula (13). In this case, the epoxy group in the (meth) acrylate having an epoxy group represented by the general formula (7) is added to the carboxyl group in the polycarboxylic acid represented by the general formula (14) by a relatively preferable amount of 10 to 50 mol%, and more preferably 30 to 50 mol%.
When the total of the repeating units (m, o, p) in the (meth) acrylate resin represented by the general formula (13) is 100, the number of the repeating units (m, o, p) may be arbitrarily changed depending on the purpose of adjusting the acid value and the curing property. The above repeating unit (m) is more preferably 20 to 70, more preferably 30 to 60, the above repeating unit (o) is more preferably 5 to 70, more preferably 10 to 50, and the repeating unit (p) is more preferably 10 to 75, more preferably 20 to 60. When m is 20 to 70, the content of polymerizable double bonds is reduced, and the decrease in adhesion and the decrease in hardness of the cured film can be suppressed. When o is 10 to 50, the solubility in an organic solvent can be improved without excessively increasing the water absorption of the cured film. When p is 10 to 40, the volume shrinkage during curing does not become too large, and thus the adhesion to the substrate and the surface flatness can be improved.
The weight average molecular weight (Mw) of the (meth) acrylate resin represented by the general formula (13) is 6000 or more, preferably 6000 or more and 1000000 or less, and more preferably 10000 or more and 100000 or less. When the weight average molecular weight (Mw) is 6000 or more, the resin phase is separated from the alkali-soluble resin, and a thin layer (10 to 100nm) is formed on the outermost layer side (surface not in contact with the substrate) of the cured film, so that the reflectance can be reduced without providing an antireflection film or the like on the outermost layer side (surface not in contact with the substrate) of the cured film. Further, when 1000000 or less, the decrease in adhesion and the decrease in curing properties can be suppressed.
The acid value of the (meth) acrylate resin represented by the general formula (13) is preferably 30mg/KOH or more and 200mg/KOH or less, and more preferably 40mg/KOH or more and 140mg/KOH or less. When the acid value of the (meth) acrylate resin is 30mg/KOH or more, a residue is hardly left in the alkali development. In addition, when the content is 200mgKOH/g or less, the penetration of the alkali developing solution is not too fast, and thus the peeling development can be suppressed.
The weight average molecular weight (Mw) and acid value of the (meth) acrylate resin represented by the above general formula (13) can be measured by the same measuring apparatus as that used for the alkali-soluble resin represented by the general formula (1).
The mass of the (meth) acrylate resin represented by the general formula (13) is more preferably 1 to 60 mass%, more preferably 10 to 60 mass%, and still more preferably 20 to 60 mass% with respect to the total mass of the alkali-soluble resin represented by the general formula (1) and the (meth) acrylate resin represented by the general formula (13). When the mass of the (meth) acrylate resin is 1 to 60 mass%, a crosslinked structure is sufficiently formed, and thus a cured film after curing is not easily weakened.
(light screening Material)
The light-shielding material of component (iii) in one embodiment of the present invention is selected from the group consisting of a black organic pigment, a black inorganic pigment, and a mixed color organic pigment.
The light-shielding material usable in the present invention is not particularly limited, and any known light-shielding component can be used as long as it is dispersed in an average particle diameter of 1 to 1000 nm. The average particle diameter of the light shielding material can be measured by, for example, a laser diffraction scattering particle diameter distribution meter or a dynamic light scattering particle diameter distribution meter.
Examples of the above black organic pigments include perylene black, indigo black, aniline black, lactam black, and the like.
Examples of the black inorganic pigment include carbon black, chromium oxide, iron oxide, titanium black, and the like.
Examples of the color-mixed organic pigment include mixed pigments in which at least 2 color pigments selected from organic pigments such as azo pigments, condensed azo pigments, methine azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, vat pigments, perylene pigments, perinone pigments, quinolinone pigments, pyrrolopyrrole dione pigments, thioindigo pigments, and the like are mixed and blackened.
The light shielding material may be used alone in 1 kind or in combination in 2 or more kinds depending on the function of the desired photosensitive resin composition. For example, carbon black, titanium black, black organic pigments, etc. can be used as a light-shielding resist used for manufacturing a black matrix of a color filter, red, orange, yellow, green, blue, violet organic pigments, etc. can be used as a coloring resist used for manufacturing pixels of a color filter, organic pigments, inorganic fillers, etc. can be used as a solder resist used for manufacturing an insulating film of a printed wiring board, carbon black, titanium black, black organic pigments, white pigments, etc. can be used as a decorative resist used for designing a front glass of a touch panel, and transparent fillers such as silica, etc. can be used as a transparent resist having high hardness and high durability, and can be selected and used as appropriate.
When a mixed color organic pigment is used as the component (iii), examples of the organic pigment that can be used include, but are not limited to, those having the color material index name shown below.
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, etc.;
Pigment orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.;
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 15, 15: 1. 15: 2. 15: 3. 15: 4. 15: 6. 16, 60, 80, etc.;
pigment violet 19, 23, 37, and the like.
The content of the light-shielding material may be arbitrarily determined depending on the desired degree of light shielding, but 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 a black organic pigment such as aniline black, indigo black, or lactam black, or a black inorganic pigment such as carbon black or titanium black is used as the light shielding material, it is particularly preferably 40 to 60% by mass based on the solid content in the photosensitive resin composition. When the light-shielding material content is 20% by mass or more relative to the solid content in the photosensitive resin composition, sufficient light-shielding properties can be obtained. In addition, if the light-shielding material content is 80% by mass or less with respect to the solid content in the photosensitive resin composition, the content of the photosensitive resin which originally becomes the binder is not reduced, and the required development characteristics and film forming ability can be obtained.
The light-shielding material is usually mixed with other blending components as a light-shielding material dispersion dispersed in a solvent, and in this case, a dispersant may be added. The usable dispersing agent is not particularly limited, and known compounds (compounds commercially available under the names of dispersing agents, dispersion wetting agents, dispersion accelerators, and the like) for dispersing a pigment (light shielding material) and the like can be used.
Examples of the dispersant include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative type 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 1 to 100mgKOH/g and a number average molecular weight (Mn) of 1000 to 100000, in view of an adsorption point to the colorant. The content of the dispersant is more preferably 1 to 35% by mass, and still more preferably 2 to 25% by mass, relative to the total mass of the light-shielding material. In addition, high-viscosity substances such as resins generally have an effect of stabilizing dispersion, but are not regarded as dispersants if they do not have a dispersion accelerating ability. However, the dispersion is not limited to use for the purpose of stable dispersion.
(photopolymerizable monomer)
The photosensitive resin composition according to one embodiment of the present invention is preferably a photopolymerizable monomer having at least 2 polymerizable unsaturated groups, which contains the component (iv).
Examples of the above photopolymerizable monomers 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, 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, ethylene oxide-modified hexa (meth) acrylate of phosphazene, and mixtures thereof, Caprolactone-modified (meth) acrylates such as dipentaerythritol hexa (meth) acrylate, and dendrimers having a (meth) acryloyl group as compounds having an ethylenic double bond. These monomers may be used alone in 1 kind or in combination in 2 or more kinds.
The photopolymerizable monomer has an effect of crosslinking the alkali-soluble resin molecules with each other, and in order to exhibit this function, it preferably has at least 2 ethylenically unsaturated bonds, and more preferably has 3 or more ethylenically unsaturated bonds. Further, the equivalent weight of acrylic acid obtained by dividing the molecular weight of the monomer by the number of (meth) acryloyl groups in 1 molecule is more preferably 50 to 300g/eq, and the equivalent weight of acrylic acid is more preferably 80 to 200 g/eq. The photopolymerizable monomer does not have a free carboxyl group.
In addition, a dendrimer having a (meth) acryloyl group may be used as the compound having an ethylenically unsaturated bond. Examples of the dendritic polymer include dendritic polymers 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 resin composition includes a dendritic polymer obtained by reacting a (meth) acryloyl group of a polyfunctional (meth) acrylate represented by the general formula (16) with a polyvalent mercapto compound represented by the general formula (17), and the like.
Figure BDA0002998701700000171
(in the formula (16), R14Is a hydrogen atom or a methyl group, R15Is R16(OH)kN of the k hydroxyl groups of (a) participate in the remaining part after the ester bond in the formula (b). More preferred R 16(OH)kThe polyol is a polyol having a linear or branched non-aromatic hydrocarbon skeleton having 2 to 8 carbon atoms, a polyol ether in which a plurality of molecules of the polyol are connected to each other through an ether bond by dehydration condensation of the alcohol, or an ester of the polyol or the polyol ether and a hydroxy acid. )
Figure BDA0002998701700000172
(in the formula (17), R17Is a single bond or a 2 to 6 valent C1 to C6 hydrocarbon group at R17R is 2 when it is a single bond, in R17And r is an integer of 2 to 6 when it is a 2 to 6 valent group. )
In addition, q represented by the general formula (16) and r represented by the general formula (17) independently represent an integer of 2 to 20, and q.gtoreq.r.
Examples of the polyfunctional (meth) acrylate represented by the above general formula (16) 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 in 1 kind or in combination of 2 or more kinds.
Examples of the polyvalent mercapto compound represented by the above general formula (17) 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 in 1 kind or in combination of 2 or more kinds.
(i) The blending ratio of the component (i) to the component (iv) is preferably 50/50 to 90/10, more preferably 60/40 to 80/20 in terms of the weight ratio (i)/(iv). (i) When the blending ratio of the component (a) is 50/50 or more, the cured product after photo-curing is less likely to become brittle, and the acid value of the coating film in the unexposed portion is less likely to become low, so that the lowering of the solubility in an alkali developing solution can be suppressed. Therefore, the pattern edge is less likely to be formed into a jagged shape or a sharp shape. When the blending ratio of the component (i) is 90/10 or less, the ratio of the photoreactive functional group to the resin is sufficient, and the desired crosslinked structure can be formed. Further, since the acid value of the resin component is not excessively high, the solubility in an alkali developing solution in an exposed portion is not easily increased, and the pattern formed is prevented from becoming thinner than a target line width or from being damaged.
(photopolymerization initiator)
The photosensitive resin composition according to one embodiment of the present invention is preferably a photopolymerization initiator containing the component (v).
Examples of the above photopolymerization initiator include: acetophenones such as acetophenone, 2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone and p-tert-butylacetophenone, diphenylketones such as diphenylketone, 2-chlorodiphenylketone and p, p' -bisdimethylaminodiphenylketone; benzoin ethers such as diphenylethanedione, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 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-cyanobenzyl) -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, halomethyl-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- (phenylsulfanyl) phenyl ] -,2- (O-benzoyloxime), 1- (4-phenylsulfanyl) butane-1, 2-dione-2-oxime-O-benzoate, o-acyloxime-based compounds such as 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-carbazolo-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 and the like; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine. These photopolymerization initiators may be used alone in 1 kind or in combination in 2 or more kinds.
In particular, when a photosensitive resin composition containing a colorant is formed, it is preferable to use O-acyloxime compounds (including ketoximes). Examples of the group of compounds that can be used are preferably O-acyloxime photopolymerization initiators represented by the general formulae (18) and (19). Of these compounds, the use of an O-acyloxime-based photopolymerization initiator having a molar absorption coefficient of at least 10000 at 365nm is more preferable when a colorant is used at a high pigment concentration and when a cured film pattern is formed. In addition, "photopolymerization initiator" used in the present invention includes a sensitizer. The molar absorption coefficient can be measured, for example, by using an ultraviolet visible near infrared spectrophotometer "UH 4150" (manufactured by hitachi-rightech Co., Ltd.).
Figure BDA0002998701700000191
(in formula (18), R18、R19Independently represent an alkyl group of C1 to C15, an aryl group of C6 to C18, an arylalkyl group of C7 to C20 or a heterocyclic group of C4 to C12, R20Represents an alkyl group of C1 to C15, an aryl group of C6 to C18, an arylalkyl group of C7 to C20. Here, the alkyl group and the aryl group may be substituted with an alkyl group of C1 to C10, an alkoxy group of C1 to C10, an acyl group of C1 to C10, 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. )
Figure BDA0002998701700000201
(in formula (19), R21And R22Independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a cycloalkylalkyl or alkylcycloalkyl group, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. R23Each independently represents a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, a part of which is-CH2The-group may be substituted by an-O-group. In addition, these R21To R23A part of hydrogen atoms in the group may be substituted with halogen atoms. )
The content of the photopolymerization initiator of the component (v) is more preferably 3 to 30 parts by weight, and still more preferably 5 to 20 parts by weight, based on 100 parts by weight of the total of the components (i) and (iv). (v) When the blending ratio of the component (a) is 3 parts by weight or more, the sensitivity is good and a sufficient photopolymerization rate can be obtained. (v) When the blending ratio of the component is 30 parts by weight or less, the sensitivity is appropriate, and the line width and the edge of the pattern can be obtained.
(photosensitive resin composition)
The components (i) to (v) are mixed and dispersed by an appropriate method, whereby a dispersion liquid used for the photosensitive resin composition can be prepared.
(solvent)
In the photosensitive resin composition of the present invention, it is preferable to use a solvent as the component (vi) in addition to the components (i) to (v). Examples of the solvent include: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α -and β -terpineol; ketones such as acetone, Methyl ethyl ketone, cyclohexanone, and N-Methyl-2-pyrrolidone (Methyl 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; ethyl acetate, butyl acetate, celluloid threoacetate, ethyl celluloid threoacetate, butyl celluloid threoacetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and other acetates. These can be dissolved and mixed singly or in combination of 2 or more kinds to form a composition in a uniform solution state.
The photosensitive resin composition of the present invention may optionally contain a resin other than the component (i) such as an epoxy resin, a curing agent, a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a surfactant, a coupling agent, and other additives.
Examples of the thermal polymerization inhibitor and the antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butyl catechol, phenothiazine, hindered phenol compounds, and the like.
Examples of the above plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate and the like.
Examples of the filler include glass fiber, silica, mica, alumina, and the like.
Examples of the defoaming agent or leveling agent include silicone-based, fluorine-based, and acrylic-based compounds. Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, and the like.
Examples of the above-mentioned coupling agent include 3- (glycidoxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane and the like.
In the photosensitive resin composition of the present invention, the total amount of the alkali-soluble resin of component (i), the (meth) acrylic resin of component (ii), the light-shielding material of component (iii), the photopolymerizable monomer of component (iv), and the photopolymerization initiator of component (v) in the solid components other than the solvent of component (vi) (the solid components include monomers which become solid components after curing) is preferably 80 mass% or more, and more preferably 90 mass% or more. The amount of the solvent varies depending on the target viscosity, but is preferably 40 to 90% by mass relative to the whole amount.
For example, 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 light, radiation, and the like), thereby obtaining a cured film obtained by curing the photosensitive resin composition of the present invention. The desired pattern can be obtained by setting the irradiated portion and the non-irradiated portion using a mask or the like, hardening only the irradiated portion, and dissolving the other portion with an alkali solution.
In addition, the cured film obtained by curing the photosensitive resin composition of the present invention can be used as a black matrix for a color filter. For example, the transparent substrate is formed with a cured film having a film thickness of 1.0 to 2.0 μm, the cured film is formed, then, red, blue, and green pixels are formed by photolithography, and red, blue, and green inks are applied to the cured film by an ink jet process.
The cured film obtained by curing the photosensitive resin composition of the present invention can be used as a black column spacer for a liquid crystal display device. For example, a single black resist may be used to form a plurality of portions having different film thicknesses, one of which functions as a spacer and the other of which functions as a black matrix.
Specifically, each step of the method of forming a cured film by coating and drying the photosensitive resin composition according to one embodiment of the present invention will be described.
The method for applying the photosensitive resin composition to the substrate may be any of known methods such as a solution dipping method, a spraying method, a method using a roll coater, a link coater, a slit coater, and a rotary coater. After coating to a desired thickness by these methods, the coating film is formed by removing the solvent (prebaking). 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 carried out at 80 to 120 ℃ for 1 to 10 minutes, for example.
The radiation used for the exposure may be, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like, but the wavelength range of the radiation is preferably 250 to 450 nm. For the developer suitable for the alkali development, an aqueous solution of sodium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, or the like can be used. These developers may be appropriately selected depending on the characteristics of the resin layer, but it is also effective to add a surfactant if necessary. The developing temperature is preferably 20 to 35 ℃, and a fine image can be formed precisely using a commercially available developing machine, an ultrasonic washing machine, or the like. In addition, the alkali development is usually followed by water washing. The developing method may be a shower developing method, a spray developing method, a dip developing method, a barrel (liquid) developing method, or the like.
After development in this manner, heat treatment (post-baking) is carried out at 180 to 250 ℃ for 20 to 100 minutes. The post baking is performed to improve adhesion between the patterned hard film (hard film) and the substrate. The baking is performed by heating with an oven, a hot plate, or the like, as in the case of prebaking. The patterned hard film (hard film) of the present invention is formed through each step by photolithography. Then, polymerization or curing (both are referred to as curing) is thermally terminated to obtain a cured film having a desired pattern. The curing temperature at this time is more preferably 160 to 250 ℃.
In the cured film obtained by the above method, the alkali-soluble resin containing a polymerizable unsaturated group and the (meth) acrylate resin are subjected to phase separation, and a thin layer is formed on the outermost layer (surface not in contact with the substrate) on the cured film side. As a result, a cured film having a reduced reflectance can be easily obtained without using a resin having a reduced refractive index and without providing an antireflection film or the like on the outermost layer (surface not in contact with the substrate) of the cured film to be formed.
(examples)
The following specifically describes embodiments of the present invention with reference to examples and comparative examples, but the present invention is not limited to these examples.
The following description explains synthesis examples of (i) an alkali-soluble resin represented by general formula (1) and (ii) a (meth) acrylate resin represented by general formula (13), and resin evaluation in these synthesis examples is performed in the following manner unless otherwise specified. When the same model is used for each measurement instrument, the machine manufacturer name is omitted from the 2 nd appearance. In the examples, all of the glass substrates used for producing the substrate with the cured film for measurement were treated in the same manner.
[ solid concentration ]
A glass filter was impregnated with 1g of the resin solution obtained in synthesis example (weight: w0(g) And weighing [ W ]1(g) The weight [ W ] of the steel sheet heated at 160 ℃ for 2 hours was determined from the following formula (1)2(g)〕。
Solid content (wt%) < 100 × (W)2-W0)/(W1-W0)...(1)。
[ 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 ]
The weight average molecular weight (Mw) was determined as a conversion value of standard polystyrene (PS-Oligomer Kit manufactured by TOSOH Co., Ltd.) by colloidal permeation chromatography (GPC) "HLC-8220 GPC" (manufactured by TOSOH Co., Ltd., solvent: tetrahydrofuran, column: TSKgelSuperH-2000(2 pieces) + TSKgelSuperH-3000(1 pieces) + TSKgelSuperH-4000(1 pieces) + TSKgelSuperH-5000(1 pieces)) (manufactured by TOSOH Co., Ltd., temperature: 40 ℃ C., speed: 0.6 ml/min).
The synthesis examples used are abbreviated as follows.
BPFE: a fluorene-9, 9-diyl compound (a reactant of 9, 9-bis (4-hydroxyphenyl) fluorene with epichlorohydrin (epoxy equivalent 250 g/eq)).
AA: acrylic acid.
BPDA: 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride.
THPA: tetrahydrophthalic anhydride.
TEAB: tetraethylammonium bromide.
PGMEA: propylene glycol monomethyl ether acetate.
MAA: methacrylic acid.
MMA: methyl methacrylate.
CHMA: cyclohexyl methacrylate.
GMA: glycidyl methacrylate.
AIBN: azobisisobutyronitrile.
TPP: triphenylphosphine.
[ Synthesis example 1]
(alkali-soluble resin)
BPFE (224.00g, 0.45 mol), AA (64.57g, 0.90 mol), PGMEA (43.27g), TEAB (0.94g), 2, 6-di-t-butyl-p-cresol (0.10g) were charged in a 1000ml four-necked flask equipped with a reflux condenser, stirred at 100 to 105 ℃ for 20 hours and reacted. Then, PGMEA (246.32g), BPDA (65.90g, 0.225 mol) and THPA (34.08g, 0.225 mol) were added thereto, and the mixture was stirred at 120 to 125 ℃ for 6 hours to obtain an alkali-soluble resin (i) (solid content: 56.5 wt%, weight average molecular weight (Mw): 3600, acid value (in terms of solid content): 99.5 mgKOH/g).
[ Synthesis example 2]
((meth) acrylate resin)
MAA (61.98g, 0.72 mol), MMA (43.25g, 0.43 mol), CHMA (48.45g, 0.29 mol), AIBN (7.09g), and diethylene glycol dimethyl ether (432g) were charged into a 1000ml four-necked flask equipped with a nitrogen introduction tube and a reflux condenser, and the mixture was stirred at 80 to 85 ℃ for 8 hours under a nitrogen stream and polymerized. In addition, GMA (73.69g, 0.52 mol), TPP (1.76g), and 2, 6-di-t-butyl-p-cresol (0.10g) were charged into the four-necked flask, and the mixture was stirred at 80 to 85 ℃ for 16 hours to obtain a (meth) acrylate resin (ii) (solid content: 35.5 mass%, weight average molecular weight (Mw): 21500, and acid value (in terms of solid content): 50 mgKOH/g).
[ Synthesis example 3]
((meth) acrylate resin)
A1000 ml four-necked flask equipped with a nitrogen inlet tube and a reflux condenser was charged with MAA (61.98g, 0.72 mol), MMA (43.25g, 0.43 mol), CHMA (48.45g, 0.29 mol), AIBN21.28g, and diethylene glycol dimethyl ether (458g), and the mixture was stirred at 80 to 85 ℃ under a nitrogen stream for 8 hours and polymerized. GMA (73.69g, 0.52 mol), TPP1.76g, and 0.10g of 2, 6-di-t-butyl-p-cresol were charged into the four-necked flask, and the mixture was stirred at 80 to 85 ℃ for 16 hours to obtain (meth) acrylate resin (ii) -2 (solid content: 35.6 mass%, weight average molecular weight (Mw): 6500, acid value (in terms of solid content): 52 mgKOH/g).
[ comparative Synthesis example 1]
((meth) acrylate resin)
MMA (84.10g, 0.84 mol), CHMA (141.41g, 0.84 mol), AIBN8.28g, and diethylene glycol dimethyl ether (430g) were charged into a 1000ml four-necked flask equipped with a nitrogen introduction tube and a reflux condenser, and stirred at 80 to 85 ℃ for 8 hours under a nitrogen stream to obtain (meth) acrylate resin (ii) -3 (solid content: 35.3 mass%, weight average molecular weight (Mw): 19300).
The photosensitive resin compositions of examples 1 to 4 and comparative examples were prepared in the blending amounts (values are% by mass) shown in table 1. The blending ingredients used in the table are as follows.
(i) The method comprises the following steps The alkali-soluble resin obtained in example 1 was synthesized.
(ii) -1: the (meth) acrylate resin obtained in Synthesis example 2.
(ii) -2: the (meth) acrylate resin obtained in Synthesis example 3.
(ii) -3: the (meth) acrylate resins obtained in Synthesis example 1 were compared.
(iii) The method comprises the following steps 20.0% by mass of carbon black, and 5.0% by mass of a polymer dispersant (solid content: 25.0%, average secondary particle diameter of carbon black: 162 nm).
(iv) The method comprises the following steps Dipentaerythritol hexaacrylate.
(v) The method comprises the following steps Irgacure OXE02 (manufactured by BASF JAPAN, Inc.; Irgacure is a registered trademark of the same company).
(vi) The method comprises the following steps Propylene glycol monomethyl ether acetate.
[ Table 1]
Composition (I) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2
(i) 10.9 9.5 8.2 6.8 9.5 13.6 6.8
(ii)-1 4.3 6.5 8.7 10.8
(ii)-2 6.5
(ii)-3 10.9
(iii) 35.0 35.0 35.0 35.0 35.0 35.0 35.0
(iv) 2.6 2.6 2.6 2.6 2.6 2.6 2.6
(v) 0.7 0.7 0.7 0.7 0.7 0.7 0.7
(vi) 46.5 45.7 44.8 44.1 45.7 48.1 44.0
Total up to 100 100 100 100 100 100 100
[ evaluation ]
The following evaluations were carried out using the photosensitive resin compositions of examples 1 to 5 and comparative examples 1 to 2. In addition, the glass substrate used for producing the hardened film for evaluation was a glass substrate which was all subjected to the same treatment.
(preparation of cured film for evaluation of adhesion and straightness)
Irradiating with low pressure mercury lamp at 254nm to obtain illumination of 1000mJ/cm2And a 125mm × 125mm glass substrate "# 1737" (manufactured by Corning Corp.) having a surface cleaned with ultraviolet rays (hereinafter referred to as "UV light source") " Glass substrate "), a photosensitive resin composition shown in table 1 was coated with a spin coater so that the film thickness after the heat curing treatment became 1.5 μm, and prebaked with a hot plate at 90 ℃ for 1 minute to prepare a cured film. Then, using a negative photomask for pattern formation with an i-line illuminance of 30mW/cm2The high-pressure mercury lamp (2) is irradiated with ultraviolet rays having a wavelength of 365nm and exposed.
The exposed cured film was subjected to development treatment using a 0.15% aqueous sodium carbonate solution at 23 ℃ and then subjected to main curing (post-baking) using a hot air dryer at 230 ℃ for 30 minutes, thereby obtaining cured films of examples 1 to 5 and comparative examples 1 to 2.
[ evaluation of adhesion ]
(evaluation method)
The line width of the pattern after the final hardening (post-baking) was confirmed by an optical microscope "ECLIPSE LV 100" (manufactured by Nikon corporation).
(evaluation criteria)
O: a pattern having an L/S (line width/space width) of 20 μm/20 μm or more can be formed without leaving any residue.
X: no pattern with L/S (line width/space width) of less than 20 μm/20 μm was formed, or stringiness or residue was evident in the pattern.
[ evaluation of straightness ]
(evaluation method)
The linearity of the fine line pattern of the cured film after the final curing (post-baking) was confirmed by an optical microscope "ECLIPSE LV 100".
(evaluation criteria)
O: peeling or chipping of the fine line pattern from the glass substrate and jaggy pattern edges were not observed.
X: peeling or chipping of the thin line pattern from the glass substrate and jagged pattern edges were observed.
(preparation of cured film for evaluation of reflectance, optical Density, and appearance)
The photosensitive resin compositions shown in table 1 were applied onto a glass substrate using a spin coater so that the film thickness after the heat curing treatment became 1.5 μm, and prebaked for 1 minute at 90 ℃ using a hot plate to prepare cured films. However, the device is not suitable for use in a kitchenThen, the i-line illuminance was 30mW/cm without using a negative photomask for pattern formation2The high-pressure mercury lamp (2) is exposed to ultraviolet light having a wavelength of 365 nm.
[ evaluation of reflectance ]
(evaluation method)
The substrate with the cured film for reflectance evaluation was measured for reflectance on the cured film side (the side opposite to the glass substrate) at an incident angle of 2 ° using an ultraviolet visible near infrared spectrophotometer "UH 4150" (manufactured by hitachi-rightech corporation).
(evaluation criteria)
Very good: the surface of the cured film has a reflectance of 5.5 or less.
O: the surface of the cured film has a reflectance of more than 5.5 and 6.5 or less.
And (delta): the surface of the cured film has a reflectance of more than 6.5 and 7.5 or less.
X: the reflectance of the surface of the cured film exceeds 7.5.
The exposed cured film was subjected to development treatment using a 0.15% aqueous sodium carbonate solution at 23 ℃ and then subjected to main curing (post-baking) using a hot air dryer at 230 ℃ for 30 minutes, thereby obtaining cured films of examples 1 to 5 and comparative examples 1 to 2.
[ evaluation of optical Density ]
(evaluation method)
The Optical Density (OD) of the cured film produced in the same manner as the cured film for Optical Density (OD) evaluation was evaluated using a MACBETH penetrometer. The thickness of the cured film formed on the substrate was measured, and the value obtained by dividing the Optical Density (OD) value by the thickness was defined as OD/. mu.m.
The Optical Density (OD) is calculated by the following formula (1).
The optical concentration (OD) — log10T (1).
(T represents a transmittance.)
[ appearance evaluation ]
The presence or absence of unevenness and foreign matter on the surface of the cured film of the substrate with the cured film for appearance evaluation was visually observed.
(evaluation criteria)
Very good: no whitening, color unevenness or foreign matter was observed at all.
O: whitening, color unevenness or foreign matter was observed in the area below 1/4 of the surface.
And (delta): whitening, color unevenness or foreign matter was observed in the area below 1/3 of the surface.
X: whitening, color unevenness or foreign matter was observed as a whole.
The evaluation results are shown in Table 2.
[ Table 2]
Figure BDA0002998701700000281
From the results of examples 1 to 5 and comparative examples 1 to 2, it is understood that the use of the photosensitive resin composition containing the alkali-soluble resin (i) and the (meth) acrylate resin (ii) according to the present invention can reduce the reflectance on the cured film side, and can achieve both high light-shielding properties and formation of a high-definition pattern.
Further, it is found that by using 2 different types of resins, a photosensitive resin composition which can reduce the reflectance by a simple method and can achieve both high light-shielding properties and formation of a high-definition pattern can be obtained.
(Industrial Applicability)
The photosensitive resin composition of the present invention can provide a photosensitive resin composition having high light-shielding properties and low reflectance, and a cured film and a color filter using the photosensitive resin composition. The cured film of the present invention can realize low reflection on the coating surface side of the cured film when formed on a transparent substrate, and therefore, can be used as a cured film for sensors such as various display devices and image sensors.

Claims (7)

1. A photosensitive resin composition contains, as resin components:
an alkali-soluble resin (i) containing a polymerizable unsaturated group, which is obtained by reacting a reactant of an epoxy compound having 2 or more phenylglycidyl ether groups in the molecule and a monocarboxylic acid containing an unsaturated group, with a dicarboxylic acid or a tricarboxylic acid or an acid monoanhydride thereof, and a tetracarboxylic acid or an acid dianhydride thereof, and has a weight-average molecular weight of 2500 or more; and
(meth) acrylate resin (ii) having a weight average molecular weight of 6000 or more, the weight average molecular weight having a carboxyl group and a polymerizable unsaturated group in a side chain thereof;
and the photosensitive resin composition contains a light-shielding material (iii) selected from the group consisting of a black organic pigment, a black inorganic pigment or a mixed color organic pigment as an essential component.
2. The photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the alkali-soluble resin (i) containing a polymerizable unsaturated group is 2500 or more and 100000 or less,
the weight average molecular weight of the (meth) acrylate resin (ii) is 6000 to 1000000,
(iii) the mass of the (ii) is 1 to 60% by mass based on the total mass of the (i) and the (ii).
3. The photosensitive resin composition according to claim 1 or 2, wherein the polymerizable unsaturated group-containing alkali-soluble resin (i) has a structure represented by the general formula (1),
Figure FDA0002998701690000011
in the formula (1), R1Independently a hydrocarbon group of carbon number 2 to 4, R2Independently a hydrocarbon group of carbon number 1 to 3, R3Independently a hydrogen atom or a methyl group, X independently is a C1-20 organic group having a valence of 2, -CO-, -SO2-、-C(CF3)2-、-CH2-、-C(CH3)2-、-Si(CH3)2-, -O-, a fluorene-9, 9-diyl group represented by the general formula (2) or a single bond, Y is a 4-valent carboxylic acid residue, Z is independently a hydrogen atom or a substituent represented by the general formula (3), but at least 1 of Z is a substituent represented by the general formula (3), G is independently a hydrogen atom or a substituent represented by the general formula (4), a is independently a number of 0 to 10, b is independently a number of 0 to 4, n is a substituent represented by the average value of 1 to 20 An integer number;
Figure FDA0002998701690000021
in the formulae (3) and (4), R4、R6Is a hydrogen atom or a methyl group, R5、R7Is a hydrocarbon group having 2 to 4 carbon atoms, L is a 2-or 3-valent carboxylic acid residue, c and f are numbers of 0 or 1, d and e are numbers of 0, 1 or 2, and d + e is a number of 1 or 2.
4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the (meth) acrylate resin (ii) is a (meth) acrylate resin having a carboxyl group and a polymerizable unsaturated group in a side chain, the (meth) acrylate resin being obtained by reacting a part of the carboxyl groups in a copolymer of a (meth) acrylate represented by general formula (5) and a (meth) acrylic acid represented by general formula (6) with a (meth) acrylate having an epoxy group represented by general formula (7),
Figure FDA0002998701690000022
in the formula (5), R8Is a hydrogen atom or a methyl group, R9Is a hydrocarbon group having 1 to 20 carbon atoms, the above-mentioned R9May contain an etheric oxygen atom or a urethane bond inside;
Figure FDA0002998701690000031
in the formula (6), R10Is a hydrogen atom or a methyl group;
Figure FDA0002998701690000032
in the formula (7), R11Is a hydrogen atom or a methyl group, R12Is a 2-valent hydrocarbon group having 2 to 10 carbon atoms, and g is a number of 0 or 1.
5. The photosensitive resin composition according to any one of claims 1 to 4, further comprising as essential components:
(iv) a photopolymerizable monomer having at least 2 polymerizable unsaturated groups; and
(v) A photopolymerization initiator.
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 of claim 6 as a black matrix.
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