CN111752096B - Photosensitive resin composition for color filter and color filter - Google Patents

Photosensitive resin composition for color filter and color filter Download PDF

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CN111752096B
CN111752096B CN201910248409.8A CN201910248409A CN111752096B CN 111752096 B CN111752096 B CN 111752096B CN 201910248409 A CN201910248409 A CN 201910248409A CN 111752096 B CN111752096 B CN 111752096B
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photopolymerization initiator
acid
photosensitive resin
composition
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CN111752096A (en
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钱晓春
杨金梁
严春霞
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Changzhou Zhengjie Intelligent Manufacturing Technology Co ltd
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Changzhou Zhengjie Intelligent Manufacturing Technology Co ltd
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Priority to PCT/CN2020/081284 priority patent/WO2020200018A1/en
Priority to KR1020217035481A priority patent/KR102649509B1/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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—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
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • 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
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—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
    • 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
    • G03F7/20—Exposure; Apparatus therefor

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Optical Filters (AREA)

Abstract

The invention discloses a photosensitive resin composition for a color filter, the color filter and a manufacturing method thereof. The composition comprises a photopolymerization initiator, an alkali-soluble resin, a compound having at least one polymerizable unsaturated bond, a colorant and a hydrogen donor, and has excellent sensitivity and good developability in application, high brightness after curing, and excellent adhesion to a substrate.

Description

Photosensitive resin composition for color filter and color filter
Technical Field
The invention belongs to the technical field of organic chemistry and photocuring, and particularly relates to a photosensitive resin composition for a color filter, a color filter using the photosensitive resin composition and a manufacturing method of the color filter.
Background
The color filter is generally manufactured by forming red, green, blue, and other color elements on a transparent substrate by a dyeing method, a printing method, a pigment dispersion method, and the like. The pigment dispersion method is currently the mainstream of the industrial method, and a color filter is formed by coating a photosensitive resin composition containing a colorant on a transparent substrate, followed by image exposure, development and, optionally, post-curing, and repeating these processes. The method has the advantages of high heat resistance, no need of dyeing, and high precision of forming a colored layer.
In recent years, there has been an increasing demand for color filters in terms of chromaticity, contrast, and the like. In order to achieve high color purity of a display element or high color resolution of a light-receiving element, the concentration of a colorant in a composition tends to be high, but this also poses problems, including: residues or stains are likely to be generated on the base or the light-shielding layer of the unexposed portion during the development process, adhesion to the substrate becomes insufficient, sufficient hardening cannot be obtained, or pattern formability is poor in the exposed portion.
To date, the combination/selection of components for photosensitive resin compositions has been the main means for obtaining products having more excellent application properties.
Disclosure of Invention
In view of the needs of the prior art, it is an object of the present invention to provide a photosensitive resin composition for a color filter, which has excellent sensitivity and good developability when applied, has high brightness after curing, and has excellent adhesion to a substrate.
In order to achieve the purpose, the following specific technical scheme is adopted.
A photosensitive resin composition for a color filter, comprising the following components:
(A) A photopolymerization initiator comprising a photopolymerization initiator A1 and at least one oxime ester photoinitiator A2;
(B) An alkali soluble resin;
(C) A compound having at least one polymerizable unsaturated bond;
(D) A colorant;
(E) A hydrogen donor;
wherein the photopolymerization initiator A1 is Hexaarylbisimidazole (HABI) mixed photoinitiator, has a structure shown in a general formula (I), contains 2-1', 2-3', 2'-1 and 2' -3 four-connection-site bisimidazole compounds, and the total mass percentage content of the four-connection-site bisimidazole compounds in A1 is more than 92%,
Figure BDA0002011685900000021
in the general formula (I), ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 May be the same or different and each independently represents a substituted or unsubstituted aryl group;
and the photopolymerization initiator (A) has a molar extinction coefficient at i-line (365 nm) of 5000-10000.
Another object of the present invention is to provide a color filter using the photosensitive resin composition and a method for manufacturing the same.
Detailed Description
Hereinafter, the photosensitive resin composition, the color filter and the method for manufacturing the same according to the present invention will be described in more detail.
< photopolymerization initiator (A) >
Photopolymerization initiator A1
As described above, the photopolymerization initiator A1 of the invention is a HABI type mixed photoinitiator, has a structure shown in a general formula (I), and contains 2-1', 2-3', 2'-1 and 2' -3 four kinds of double imidazole compounds of connecting sites, and the total mass percentage content of the four kinds of double imidazole compounds of connecting sites in the photopolymerization initiator A1 is more than 92%,
Figure BDA0002011685900000031
in the general formula (I), ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 May be the same or different and each independently represents a substituted or unsubstituted aryl group;
and the photopolymerization initiator (A) has a molar extinction coefficient at i-line (365 nm) of 5000-10000.
The bisimidazole compound satisfying four connection positions of 2-1', 2-3', 2'-1 and 2' -3 of the structure shown in the general formula (I) is specifically the following structure:
Figure BDA0002011685900000041
in the general formula (I), the aryl group is preferably a phenyl group.
The substituted aryl group may be mono-substituted or poly-substituted.
Preferably, the substituents on the aryl group may be halogen, nitro, cyano, amino, hydroxy, C 1 -C 20 Alkyl or alkenyl of, C 1 -C 8 Wherein the methylene group in each independent variable (i.e., each substituent) may be optionally substituted with oxygen, sulfur, an imine group.
More preferably, the substituents on the aryl group may be fluorine, chlorine, bromine, nitro, cyano, amino, hydroxy, C 1 -C 10 Alkyl or alkenyl of, C 1 -C 5 Wherein the methylene group in each independent variable may be optionally substituted with oxygen, sulfur, or an imine group.
Further preferably, ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 At least one of which is an aryl group having a halogen substituent. The halogen substituent can improve the color change effect in the curing process so as to enhance the identification capability of an electronic eye during development (note: the photosensitive resin layer can generate color change after exposure and form color difference with an unexposed area so as to be identified by the electronic eye, and the invention can make the color difference more obvious), thereby improving the quality of an application product. Particularly preferably, the halogen substituent is chlorine.
The applicant researches and discovers that the photoinitiation activity of the HABI compound is influenced by the electronic effect and the steric effect of a substituent on an aromatic ring of the HABI compound, and the substituent on the aromatic ring has small influence on the absorption of the HABI compound near 265nm but has large influence on the absorption of the HABI compound near 365 nm. When a conjugated system is introduced into the HABI structure, the uv absorption wavelength is shifted toward a long wavelength (i.e., a red shift phenomenon is generated) and the uv absorption intensity (i.e., molar extinction coefficient) is increased.
In the photosensitive resin composition of the present invention, the photopolymerization initiator A1 is used as an initiator, and the generated active radicals undergo chain transfer via a hydrogen donor, thereby effectively promoting the hardening of the exposed region without deactivation. This is advantageous for improving the sensitivity and brightness of the color filter.
Besides the four connection sites 2-1', 2-3', 2'-1 and 2' -3, the HABI compound shown in the general formula (I) also has connection sites 1-4', 1-5', 3-4', 3-5', 1-1', 1-3', 3-1', 3-3', 4-1', 4-3', 5-1 'and 5-3'. However, the applicant has found that a photopolymerization initiator A1 as defined above is most preferable for solving the technical problems of the present invention. The single substance of any one of the linking sites has much smaller properties than the photopolymerization initiator A1, and if the total content of these four linking sites is less than 92%, the properties tend to be significantly deteriorated.
The photopolymerization initiator A1 used in the present invention is preferably a bisimidazole compound having four types of linking sites, i.e., 2-1', 2-3', 2'-1 and 2' -3, satisfying the structure represented by the general formula (I), and the total content thereof is preferably 95% by mass or more, and more preferably a bisimidazole compound having four types of linking sites, i.e., 2-1', 2-3', 2'-1 and 2' -3, satisfying the structure represented by the general formula (I).
The applicant has studied and found that when the molar extinction coefficient of the photopolymerization initiator at i-line (365 nm) is in the range of 5000 to 10000, the photopolymerization initiator has suitable sensitivity, and does not reduce the curing speed due to insufficient sensitivity, nor cause undercut due to excessively high sensitivity.
The HABI type photoinitiators are well known in the photoresist art and can be prepared by oxidative coupling of triarylimidazoles or substituted triarylimidazoles, as described in the prior art, for example, US3784557, US4622286 and US4311783 (which are incorporated herein by reference in their entirety). On the basis of the prior art, a solvent recrystallization process is added, so that the photopolymerization initiator A1 meeting the composition requirements of the invention can be conveniently obtained. The solvent can be one or a combination of more than two of toluene, methanol, ethyl acetate, dichloromethane and water. Without limitation, the photopolymerization initiator A1 can also be prepared as described in applicants' prior application (application No. 201811451262.4), which is incorporated herein by reference in its entirety.
Illustratively, the photopolymerization initiator A1 corresponding to the bisimidazole compound of the four linking positions 2-1', 2-3', 2'-1 and 2' -3 is selected from or comprises at least one of the following combinations:
Figure BDA0002011685900000061
Figure BDA0002011685900000071
Figure BDA0002011685900000081
Figure BDA0002011685900000091
in the photosensitive resin composition of the present invention, the content of the photopolymerization initiator A1 is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total amount.
Oxime ester photoinitiator A2
The photopolymerization initiator in the photosensitive resin composition of the present invention contains at least one oxime ester photoinitiator A2 in addition to the photopolymerization initiator A1.
The addition of oxime lipid photoinitiators in the system is advantageous for improving the sensitivity, resolution and the like of the composition. Compared with the method without adding the oxime lipid photoinitiator or adding other types of photoinitiators (such as acetophenone compounds, triazine compounds and the like), the method for introducing the oxime lipid photoinitiator in the presence of the photopolymerization initiator A1 can obviously improve the sensitivity and the developability of the composition, and is also favorable for improving the resolution.
The kind of the oxime ester photoinitiator is not particularly limited, and a conventionally known photoinitiator having an oxime ester group in its structure may be used. Illustratively, at least one of the following may be selected: 1- (4-phenylthiophenyl) -n-octane-1,2-dione-2-benzonate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -ethane-1-one-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -butane-1-one-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -propane-1-one-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -1-cyclohexyl-methane-1-one-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] - (3-cyclopentyl) -propane-1-one-oxime acetate, 1- (4-phenylthiophenyl) - (3-cyclopentyl) -propane-1,2-dione-2-oxime benzoate, 1- (4-phenylthiophenyl) -1,2-dione-2-oxime benzoate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -propane-1-one-oxime acetate, 1- (3-cyclohexylphenylthiophenyl) -3-oxoethyl-oxime acetate, 1-cyclohexyl-2-phenylthiobenzonate-3763-ethyl-2-oxobenzoate, and pharmaceutically acceptable salts thereof -yl ] - (3-cyclopentyl) -propane-1,2-dione-2-oxime acetate, 1- (6-o-methylbenzoyl-9-ethylcarbazol-3-yl) - (3-cyclopentyl) -propane-1,2-dione-2-oxime benzoate, 1- (4-benzoyldiphenyl sulfide) - (3-cyclopentylacetone) -1-oxime acetate, 1- (6-o-methylbenzoyl-9-ethylcarbazol-3-yl) - (3-cyclopentylacetone) -1-oxime cyclohexanoate, 1- (4-benzoyldiphenyl sulfide) -3-cyclopentylacetone) -1-oxime cyclohexanoate, and mixtures thereof 1- (6-O-methylbenzoyl-9-ethylcarbazol-3-yl) - (3-cyclopentyl) -propane-1,2-dione-oxime 2-o-methylbenzoate, 1- (4-phenylthiophenyl) - (3-cyclopentyl) -propane-1,2-dione-oxime 2-cyclohexanoate, 1- (4-thenoyl-diphenylsulfide-4' -yl) -3-cyclopentyl-propane-1-one-oxime acetate, 1- (4-benzoyldiphenylsulfide) - (3-cyclopentyl) -propane-1,2-dione -2-oxime acetate, 1- (6-nitro-9-ethylcarbazol-3-yl) -3-cyclohexyl-propan-1-one-oxime acetate, 1- (6-o-methylbenzoyl-9-ethylcarbazol-3-yl) -3-cyclohexyl-propan-1-one-oxime acetate, and pharmaceutically acceptable salts thereof 1- (6-thenoyl-9-ethylcarbazol-3-yl) - (3-cyclohexylacetone) -1-oxime acetate, 1- (6-furfurylcarboyl-9-ethylcarbazol-3-yl) - (3-cyclopentylacetone) -1-oxime acetate, processes for their preparation and their use 3425 Zxft 3425-diphenylpropane-1,3-dione-2-oxime acetate, 1- (6-furoyl-9-ethylcarbazol-3-yl) - (3-cyclohexyl) -propane-1,2-dione-2-oxime acetate, 1- (4-phenylthiophenyl) - (3-cyclohexyl) -propane-1,2-dione-2-oxime acetate, 1- (6-furfuroyl-9-ethylcarbazol-3-yl) - (3-cyclohexylacetone) -1-oxime acetate, 1- (4-phenylthiophenyl) - (3-cyclohexyl) -propane-1,2-dione -3-benzoxy benzoate, 1- (6-thenoyl-9-ethylcarbazol-3-yl) - (3-cyclohexyl) -propane-1,2-dione-2-oxime acetate, 2- [ (benzoyloxy) imino ] -1-phenylpropan-1-one, 1-phenyl-1,2-propanedione-2- (oxoacetyl) oxime, 1- (4-phenylthiophenyl) -2- (2-methylphenyl) -ethane-1,2-dione-2-oxime acetate, 1- (9,9-dibutyl-7-nitrofluoren-2-yl) -3-cyclohexyl-propane-1-one-oxime acetate, and pharmaceutically acceptable salts thereof 1- {4- [4- (thiophene-2-formyl) phenylthio ] phenyl } -3-cyclopentylpropane-1,2-dione-2-oxime acetate, 1- [9,9-dibutyl-2-yl ] -3-cyclohexylpropylpropane-1,2-dione-2-oxime acetate, 1- [6- (2-benzoyloxyimino) -3-cyclohexylpropyl-9-ethylcarbazol-3-yl ] octane-1,2-dione-2-oxime benzoate, 1- (7-nitro-9,9-diallylfluoren-2-yl) -1- (2-methof Phenylphenyl) methanone-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -3-cyclopentyl-propane-1-one-oxime benzoate, 1- [7- (2-methylbenzoyl) -9,9-dibutylfluoren-2-yl ] -3-cyclohexylpropane-1,2-dione-2-oxime acetate, 1- [6- (furan-2-formyl) -9-ethylcarbazol-3-yl ] -3-cyclohexylpropane-1,2-dione-2-ethoxycarbonyloxime ester and the like. These oxime ester compounds may be used alone or in combination of two or more.
In view of performance, the mass ratio of the photopolymerization initiator A1 to the oxime ester photoinitiator A2 in the composition is 1:5-5:5.
The content of the photopolymerization initiator (A) is 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the photosensitive resin composition. If the content of the photopolymerization initiator (a) is too small, there is a defect that photosensitivity is decreased; if the content is too large, there is a defect that the resist pattern tends to be widened beyond the line width of the photomask.
< alkali-soluble resin (B) >
In the photosensitive resin composition of the present invention, the type of the alkali-soluble resin (B) is not particularly limited, but is preferably selected from the viewpoints of heat resistance, developability, acquisition properties, and the like. The alkali-soluble resin having an acid group such as a carboxyl group or a phenolic hydroxyl group is preferable, the alkali-soluble resin of a carboxyl group-containing copolymer is more preferable, and the copolymer of an ethylenically unsaturated monomer having a carboxyl group [ hereinafter referred to as "carboxyl group-containing unsaturated monomer" (P) ] and another copolymerizable ethylenically unsaturated monomer [ hereinafter referred to as "copolymerizable unsaturated monomer" (Q) ] is particularly preferable [ hereinafter referred to as "carboxyl group-containing copolymer" (R) ].
Examples of the carboxyl group-containing unsaturated monomer (P) include the following compounds: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, alpha-chloroacrylic acid, cinnamic acid, etc.; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid, or anhydrides thereof; three or more membered unsaturated polycarboxylic acids or anhydrides thereof; mono (meth) acryloyloxyalkyl esters of dibasic or higher polycarboxylic acids such as mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, mono (2-acryloyloxyethyl) phthalate and mono (2-methacryloyloxyethyl) phthalate; and mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω -carboxy polycaprolactone monoacrylate and ω -carboxy polycaprolactone monomethacrylate. These carboxyl group-containing unsaturated monomers may be used alone or in combination of two or more.
The copolymerizable unsaturated monomer (Q) may, for example, be the following compounds: (meth) acrylate compounds such as methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate and the like; aromatic vinyl compounds such as styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether; unsaturated carboxylic acid glycidyl esters such as indene-based glycidyl acrylates and glycidyl methacrylates, e.g., indene and 1-methylindene; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; macromonomers having a monoacryl group or a monomethacryl group at the terminal of a polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane, or the like. These copolymerizable unsaturated monomers may be used alone or in combination of two or more.
As the preferable alkali-soluble resin (B), the carboxyl group-containing copolymer (R) is obtained by polymerizing (P) and (Q). More preferably, the (P) is an essential component of acrylic acid and/or methacrylic acid, and further contains at least 1 compound selected from the group consisting of succinic acid mono (2-acryloyloxyethyl) ester, succinic acid mono (2-methacryloyloxyethyl) ester, ω -carboxy polycaprolactone monoacrylate and ω -carboxy polycaprolactone monomethacrylate, and the like, as the case may be; and (Q) is at least 1 monomer selected from styrene, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer.
Specific examples of the carboxyl group-containing copolymer (R) include: (meth) acrylic acid/methyl (meth) acrylate copolymer, (meth) acrylic acid/benzyl (meth) acrylate copolymer, (meth) acrylic acid/2-hydroxyethyl (meth) acrylate/benzyl (meth) acrylate copolymer, (meth) acrylic acid/methyl (meth) acrylate/polystyrene macromonomer copolymer, (meth) acrylic acid/methyl (meth) acrylate/polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid/benzyl (meth) acrylate/polystyrene macromonomer copolymer, (meth) acrylic acid/benzyl (meth) acrylate/polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid/2-hydroxyethyl (meth) acrylate/benzyl (meth) acrylate/polystyrene macromonomer copolymer, (meth) acrylic acid/2-hydroxyethyl (meth) acrylate/benzyl (meth) acrylate/polymethyl methacrylate macromonomer copolymer, methacrylic acid/styrene/(meth) acrylate/N-phenylmaleimide copolymer, (meth) acrylic acid/succinic acid mono [2- (meth) acryloyloxyethyl ] acrylate/styrene/(meth) acrylate/N-phenylmaleimide copolymer A copolymer of (meth) acrylic acid/succinic acid mono [2- (meth) acryloyloxyethyl ] ester/styrene/(meth) acrylic acid allyl ester/N-phenylmaleimide copolymer, a copolymer of (meth) acrylic acid/styrene/(meth) acrylic acid benzyl ester/glycerin mono (meth) acrylate/N-phenylmaleimide, a copolymer of (meth) acrylic acid/ω -carboxypolycaprolactone mono (meth) acrylate/styrene/(meth) acrylic acid benzyl ester/glycerin mono (meth) acrylate/N-phenylmaleimide, and the like.
In the present invention, the alkali-soluble resin (B) may be used alone or in combination of two or more.
From the viewpoints of developability, liquid viscosity, and the like, the alkali-soluble resin is preferably a polymer having a weight average molecular weight (in terms of polystyrene measured by GPC) of 1000 to 200000, more preferably 2000 to 100000, and most preferably 5000 to 50000.
The content of the component (B) is 5 to 60 parts by mass, preferably 10 to 50 parts by mass, in 100 parts by mass of the photosensitive resin composition. If the content of the alkali-soluble resin is too small, there is a defect that adhesion to the substrate is deteriorated or alkali developability of the photocured portion is reduced; if the content of the alkali-soluble resin is too large, there is a defect that the light-shielding performance is deteriorated.
< Compound (C) having at least one polymerizable unsaturated bond >
The compound (C) having at least one polymerizable unsaturated bond in the present invention may be in the form of a monomer, an oligomer, a polymer or the like.
Examples of such a compound having at least one polymerizable unsaturated bond include: and free radical polymerizable compounds such as acrylic esters, methacrylic esters, unsaturated carboxylic acids such as itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, and salts and esters thereof, urethanes, amides, anhydrides, acrylonitrile, styrene, vinyl ethers, unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated polyurethanes.
Exemplary acrylate compounds include: methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-allyloxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, 2,2,2-trifluoroethyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, and mixtures thereof 1,3-butanediol methyl ether acrylate, butoxyethyl acrylate, beta-carboxyethyl acrylate, succinoxyethyl succinate, omega-carboxypolycaprolactone monoacrylate, trimethylsiloxyethyl acrylate, diphenyl-2-acryloxyethyl phosphate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A diacrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate, EO-modified hydrogenated bisphenol A diacrylate, PO-modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylate, EO-modified bisphenol F diacrylate, PO-modified bisphenol F diacrylate, tetrabromobisphenol A diacrylate, and mixtures thereof, tricyclodecane dihydroxymethyl diacrylate, glycerol PO modified triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, and the like.
Exemplary methacrylate-based compounds include: <xnotran> , , , , , , , , -2- , -2- , , , , , , , , , , -2- , -2- , -2- -3- , -2- -3- , -5363 zxft 5363- , -3242 zxft 3242- , -1H- , -2- , 4736 zxft 4736- , , , #400 , , , , , -2- , , , , , </xnotran> Dipentaerythritol hexamethacrylate, and the like.
Without limitation, examples of the compound (C) having at least one polymerizable unsaturated bond include compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, triallyl isocyanurate, acrylamide, N-methylolacrylamide, diacetone acrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, vinyl acetate, monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate and divinyl adipate.
The compound (C) having at least one polymerizable unsaturated bond in the present invention may be used alone, or two or more compounds may be mixed at an arbitrary ratio to improve desired characteristics.
The content of the component (C) is 5 to 50 parts by mass, preferably 10 to 30 parts by mass, in 100 parts by mass of the photosensitive resin composition. If the content of component (C) is too small, there is a defect that photosensitivity is lowered; if the content of the component (C) is too large, there is a defect that the resist pattern tends to be widened beyond the line width of the photomask.
< colorant (D) >
The kind of the colorant (D) is not particularly limited in the present invention, and pigments and dyes may be included.
The pigment may include any organic pigment, inorganic pigment or a mixture thereof commonly used in the related art.
The organic pigment is not particularly limited, and may include any general-purpose pigment used for printing inks, inkjet inks, and the like. More specifically, there may be mentioned water-soluble azo pigments, water-insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthracene pyrimidine pigments, anthanthrone pigments, indanthrone pigments, xanthone pigments, pyranthrone pigments, pyrrolopyrroledione pigments and the like. These organic pigments may be used alone or in combination of two or more.
The inorganic pigment is not particularly limited, and may include a metal compound (such as a metal oxide or a metal complex) and carbon black. More specifically, an oxide of at least one metal selected from iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. These inorganic pigments may be used alone or in combination of two or more.
Organic and inorganic pigments may also include compounds classified as pigments according to Color rendering Index (Color Index, published by the british society of dyers). More specifically, c.i. pigment yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185; c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71; c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255, 264; c.i. pigment violet 14, 19, 23, 29, 32, 33, 36, 37, 38; c.i. pigment blue 15 (15, 4, 15, etc.), 21, 28, 60, 64, 76; c.i. pigment green 7, 10, 15, 25, 36, 47, 58; c.i. pigment brown 28; c.i. pigment black 1,7, etc. Among them, c.i. pigment yellow 138, 139, 150, 185; c.i. pigment orange 38; c.i. pigment red 122, 166, 177, 208, 242, 254, 255; c.i. pigment violet 23; c.i. pigment blue 15, 6; c.i. pigment green 7, 36, 58, etc. These pigments may be used alone or in combination of two or more.
In view of the high transmittance, both of the inorganic pigment and the organic pigment, it is preferable to use the pigment as fine as possible, and the average particle diameter of the pigment is preferably 0.01 to 0.1. Mu.m, more preferably 0.01 to 0.05. Mu.m.
The content of the pigment is not particularly limited, but the content of the pigment is preferably in the range of 5 to 95 parts by weight, more preferably 10 to 90 parts by weight, based on 100 parts by mass of the total amount of the colorant. If the content of the pigment is within the above range, a color filter manufactured using the pigment can have a sufficient color region and excellent light transmittance, and a desired sensitivity is ensured.
The dye is not particularly limited, and may include: acid dyes having an acid group (e.g., sulfonic acid, carboxylic acid, etc.); salts of nitrogen-containing compounds and salts of the acid dyes; sulfonamides of said acid dyes and their derivatives; acid dyes based on azo, xanthene and/or phthalocyanine and their derivatives, etc.
The dyes are preferably compounds classified as dyes in the Color rendering Index (Color Index, published by the british society of dyers), or red, blue and violet dyes among the dyes listed in the Dyeing opinion (Color Dyeing).
Illustratively, may be a c.i. solvent dye comprising: yellow dyes such as c.i. solvent yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163, etc.; red dyes such as c.i. solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179 and the like; orange dyes, such as c.i. solvent orange 2, 7, 11, 15, 26, 41, 45, 56, 62, etc.; blue dyes such as c.i. solvent blue 5, 35, 36, 37, 44, 59, 67, 70, and the like; violet dyes such as c.i. solvent violet 8, 9, 13, 14, 36, 37, 47, 49, etc.; green dyes, such as c.i. solvent green 1,3,4, 5, 7, 28, 29, 32, 33, 34, 35, and the like. Among them, c.i. solvent yellow 14, 16, 21, 56, 151, 79, 93; c.i. solvent red 8, 49, 89, 111, 122, 132, 146, 179; c.i. solvent orange 41, 45, 62; c.i. solvent blue 35, 36, 44, 45, 70; c.i. solvent violet 13, etc.
Illustratively, may be c.i. acid dyes, including: yellow dyes such as c.i. acid yellow 1,3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 and the like; red dyes such as c.i. acid red 1,4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426, etc.; orange dyes, such as c.i. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, and the like; a blue dye such as c.i. acid blue 1,7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324, 1, 335, 340 and the like; violet dyes such as c.i. acid violet 6B, 7, 9, 17, 19, 66, etc.; green dyes such as c.i. acid green 1,3,5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109 and the like. Among them, c.i. acid yellow 42 is preferable; c.i. acid red 92; c.i. acid blue 80, 90; c.i. acid violet 66; c.i. acid green 27, etc.
Illustratively, may be c.i. direct (direct) dyes including: yellow dyes such as c.i. direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141, etc.; red dyes such as c.i. direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250 and the like; orange dyes such as c.i. direct oranges 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, etc.; blue dyes such as c.i. direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, and the like; violet dyes such as c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and the like; green dyes such as c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like.
Illustratively, there may be c.i. mordant dyes including: yellow dyes, such as c.i. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, and the like; red dyes, such as c.i. mordant red 1,2,3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95, and the like; orange dyes such as c.i. mordant oranges 3,4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc.; blue dyes such as c.i. mordant blue 1,2,3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84 and the like; violet dyes such as c.i. mordant violet 1,2,4,5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58, etc.; green dyes such as c.i. mordant green 1,3,4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like.
The above dyes may be used alone or in combination of two or more thereof.
The content of the dye is not particularly limited, but the content range of the dye is preferably 5 to 95 parts by weight, and more preferably 10 to 90 parts by weight, based on 100 parts by mass of the total amount of the colorant. If the content of the dye is within the above range, excellent sensitivity can be obtained while preventing deterioration of reliability (elution of the dye by an organic solvent after pattern formation).
The content of the colorant is not particularly limited, but the content of the colorant (D) is usually 5 to 60 parts by mass, preferably 10 to 45 parts by mass, in 100 parts by mass of the photosensitive resin composition. If the content of the colorant is within the above range, the pixel has a sufficient color density, and the absence of non-pixel portions during development is not reduced, the occurrence of residue can be reduced.
< Hydrogen donor (E) >
The photosensitive resin composition of the present invention further comprises a hydrogen donor (E) to enhance the sensitivity. The HABI compound is cracked after illumination, the generated single imidazole free matrix has larger volume, the steric effect causes the activity to be smaller, and the monomer polymerization is difficult to initiate alone, but the single imidazole free radical is easy to capture active hydrogen on a hydrogen donor to generate new active free radical to initiate the monomer polymerization.
The specific type of the hydrogen donor is not particularly limited as long as it has the above-mentioned characteristics, and examples thereof include amine compounds, carboxylic acid compounds, mercapto group-containing organic sulfur compounds, alcohol compounds, and the like. These compounds may be used alone, or in combination of two or more thereof.
Exemplary, suitable amine compounds may be: aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine and the like; aromatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethylbenzoate, N-dimethyl-p-toluidine, 4,4 '-bis (dimethylamino) benzophenone, 4,4' -bis (diethylamino) benzophenone and the like.
Exemplary of suitable carboxylic acid compounds may be: aromatic heteroacetic acid, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc.
Exemplary of suitable thiol-containing organosulfur compounds are: 2-Mercaptobenzothiazole (MBO), 2-Mercaptobenzimidazole (MBI), dodecylmercaptan, ethylene glycol bis (3-mercaptobutyrate), 1,2-propanediol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexa (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate) diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (2-mercaptopropionate), ethylene glycol bis (3-mercaptoisobutyrate), 1,2-propanediol bis (3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), octanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate), dipentaerythritol hexa (3-mercaptoisobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), 1,2-propanediol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexa (2-mercaptoisobutyrate), ethylene glycol bis (4-mercaptovalerate), 1,2-propanediol bis (4-mercaptoisovalerate) diethylene glycol bis (4-mercaptovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), dipentaerythritol hexa (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), 1,2-propanediol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), aliphatic secondary polyfunctional thiol compounds such as pentaerythritol tetrakis (3-mercaptovalerate) and dipentaerythritol hexa (3-mercaptovalerate); aromatic secondary polyfunctional thiol compounds such as bis (1-mercaptoethyl) phthalate, bis (2-mercaptopropyl) phthalate, bis (3-mercaptobutyl) phthalate, bis (3-mercaptoisobutyl) phthalate and the like.
Exemplary, suitable alcohol compounds may be: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, neopentyl alcohol, n-ethanol, cyclohexanol, ethylene glycol, 1,2-propanediol, 1,2,3-glycerol, benzyl alcohol, phenethyl alcohol, etc.
The content of the hydrogen donor (E) is 0.01 to 20 parts by weight, preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the content of the hydrogen donor is within the above range, the sensitivity of the colored photosensitive resin composition can be further ensured.
< other optional additives (F) >
Other auxiliaries commonly used in the art, including other photoinitiators and/or sensitizers, organic solvents, organic carboxylic acids, pigment dispersants, adhesion enhancers, leveling agents, development improvers, antioxidants, thermal polymerization inhibitors, and the like, may also be optionally added to the photosensitive resin composition of the present invention. In addition, a surfactant, a fluorescent whitening agent, a plasticizer, a flame retardant, an ultraviolet absorber, a foaming agent, a bactericide, an antistatic agent, a magnetic substance, a conductive material, an antifungal or antibacterial material, a porous adsorbent, a fragrant material, or the like may be added according to the use.
The other photoinitiators and/or sensitizers are different from the photopolymerization initiator A1 and the oxime ester photoinitiator A2. Without limitation, it may be selected from: bisimidazoles, triazines, coumarins, acridines, oxadiazoles, aromatic ketones, benzoin and benzoin alkyl ethers, anthraquinones, thioxanthones, and the like. These compounds may be used alone or in combination of two or more.
Exemplary bisimidazoles include: 2,2 '-bis (o-chlorophenyl) -4,4',5,5 '-tetraphenyl-diimidazole, 2,2', 5-tris (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4',5' -diphenyl-1,1 '-diimidazole, 2,2', 5-tris (2-fluorophenyl) -4- (3,4-dimethoxyphenyl) -4',5' -diphenyl-diimidazole, 2,2 '-bis (2,4-dichlorophenyl) -4,4',5,5 '-tetraphenyl-diimidazole, 2,2' -bis (2-fluorophenyl) -4- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -4',5' -Diphenyl-diimidazole, 2,2 '-bis (2-fluorophenyl) -4,4',5,5 '-tetraphenyl-diimidazole, 2,2' -bis (2-methoxyphenyl) -4,4',5,5' -tetraphenyl-diimidazole, 2,2 '-bis (2-chloro-5-nitrophenyl) -4,4' -bis (4,4-dimethoxyphenyl) -4,4 '-bis (o-chlorophenyl) -diimidazole, 4,4' -bis (2-chloro-5-nitrophenyl) -4- (4,4-dimethoxyphenyl) -5- (o-chlorophenyl) -4',5' -diphenyl-diimidazole, 2,2 '-bis (2,4-dichlorophenyl) -4,4' -bis (3,4-dimethoxyphenyl) -5,5 '-bis (o-chlorophenyl) -diimidazole, 2- (2,4-dichlorophenyl) -4- (3,4-dimethoxyphenyl) -2', 5-bis (o-chlorophenyl) -4',5' -diphenyl-diimidazole, 2- (2,4-dichlorophenyl) -2'- (o-chlorophenyl) -4,4',5,5 '-tetraphenyl-diimidazole, 2,2' -bis (2,4-dichlorophenyl) -4,4',5,5' -tetraphenyl-diimidazole and the like. These bisimidazoles may be used alone or in combination of two or more.
Exemplary triazines include: 2- (4-Ethylbiphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-methyleneoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoate, ethyl-2- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate 2-ethoxyethyl-2- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate, cyclohexyl-2- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate, benzyl-2- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate, 3- { chloro-4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid, 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoamide, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like. These triazine compounds may be used alone or in combination of two or more.
Exemplary coumarins include: 3,3 '-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-diethylaminocoumarin, 3,3' -carbonylbis (7-methoxycoumarin), 7-diethylamino-4-methylcoumarin, 3- (2-benzothiazole) -7- (diethylamino) coumarin, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one [7- (diethylamino) -4-methylcoumarin ], 3-benzoyl-7-methoxycoumarin, and the like. These coumarin compounds may be used alone or in combination of two or more.
Exemplary acridine compounds include: 9-phenylacridine, 9-p-methylphenylacridine, 9-m-methylphenylacridine, 9-o-chlorophenylacridine, 9-o-fluorophenylacridine, 1,7-bis (9-acridinyl) heptane, 9-ethylacridine, 9- (4-bromophenyl) acridine, 9- (3-chlorophenyl) acridine, 1,7-bis (9-acridine) heptane, 1,5-bis (9-acridine pentane), 1,3-bis (9-acridine) propane and the like. These acridine compounds may be used alone or in combination of two or more.
Exemplary oxadiazole compounds include: 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (naphthoyl-1-yl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxadiazole, and the like. These oxadiazole compounds may be used alone or in combination of two or more.
Exemplary aromatic ketones include: acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4 '-methylbenzene sulfide, 4-benzoyl-4' -ethyldiphenyl sulfide, 4-benzoyl-4 '-propyldiphenyl sulfide, 4,4' -bis (diethylamino) benzophenone, 4-p-tolylmercapto benzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4 '-bis (dimethylamino) benzophenone, 4,4' -bis (methyl, ethylamino) benzophenone, benzyl dimethyl ketal, benzil dimethyl ketal, alpha, alpha '-Dimethylbenzoyl ketal, alpha' -diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylbenzophenone, 2-hydroxy-2-methyl-1-p-hydroxyethyletherphenylacetone, 2-methyl-1- (4-methylmercaptophenyl) -2-morpholine-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) 1-butanone, phenylbis (2,4,6-trimethylbenzoyl) oxyphosphine, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, 2-hydroxy-1- {3- [4- (2-hydroxy-2-methyl-propionyl) -phenyl ] -1,1,3-trimethyl-inden-5-yl } -2-methyl acetone, 2-hydroxy-1- {1- [4- (2-hydroxy-2-methyl-propionyl) -phenyl ] -1,3,3-trimethyl-inden-5-yl } -2-methyl acetone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) one, and the like. These aromatic ketone compounds may be used alone or in combination of two or more.
Exemplary benzoin and benzoin alkyl ether compounds include: benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, and the like. These benzoin and benzoin alkyl ether compounds may be used alone or in combination of two or more.
Exemplary anthraquinones include: 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthracene-9,10-diethyl ester, 1,2,3-trimethylanthracene-9,10-dioctyl ester, 2-ethylanthracene-9,10-bis (methyl 4-chlorobutyrate), 2- {3- [ (3-ethyloxetan-3-yl) methoxy ] -3-oxopropyl } anthracene-9,10-diethyl ester, 9,10-dibutoxyanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-bis (3-chloropropoxy) anthracene, 9,10-bis (2-hydroxyethanethiol) anthracene, 9,10-bis (3-hydroxy-1-propanethiol) anthracene and their analogs. These anthraquinone compounds may be used alone or in combination of two or more.
Exemplary thioxanthone compounds include: thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diisopropylthioxanthone, and the like. These thioxanthone compounds may be used alone or in combination of two or more.
Illustratively, the organic solvent is not particularly limited as long as it can dissolve the aforementioned components, and may include, for example: glycol ether solvents, alcohol solvents, ester solvents, ketone solvents, amide solvents, chlorine-containing solvents, and the like. The selection is preferably made in consideration of, in particular, the solubility, coatability, safety and the like of the colorant and the alkali-soluble resin. Preferred are ethyl cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), methyl methoxybutanol (3-methyl-3-methoxybutanol), butyl carbitol (diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monoethyl ether acetate, ethyl acetate, N-butyl acetate, isobutyl acetate, cellosolve acetate (ethylene glycol monomethyl ether acetate), and mixtures thereof methoxybutyl acetate (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, ethyl 3-ethoxypropionate (EEP), methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), isophorone (3,5,5-trimethyl-2-cyclohexene-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone), N-methylpyrrolidone (4-methylaminolactam or NMP), methanol, ethanol, isopropanol, N-propanol, methyl ethyl acetate (EEP), methyl lactate (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone (4-hydroxy-4-methyl-2-pentanone), isophorone (3238, dimethyl-2-cyclohexanone, dimethyl-4-methyl-aminolactam or NMP), and N-methyl pyrrolidone (NMP), and mixtures thereof, isobutanol, n-butanol, and the like. These solvents are used alone, or in combination of two or more thereof.
Illustratively, the kind of the organic carboxylic acid is not particularly limited, and may include, for example: aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, heptanoic acid, and octanoic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, and citraconic acid; 1,2,3-aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, norkaempferoic acid, etc.; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, 2,3-dimethylbenzoic acid and 3,5-dimethylbenzoic acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, 1,2,3,5-benzenetetracarboxylic acid, and 1,2,4,5-benzenetetracarboxylic acid; and other carboxylic acids such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, umbellic acid, and the like. These organic carboxylic acids are used alone, or in combination of two or more thereof.
Illustratively, the kind of the dispersant is not particularly limited, and may include, for example: examples of the polymeric dispersant include polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic copolymers, naphthalenesulfonic acid-formaldehyde condensates, polyoxyethylene alkyl phosphates, polyoxyethylene alkylamines, alkanolamines, pigment derivatives, and the like. These dispersants are used alone, or in combination of two or more thereof.
Illustratively, the kind of the adhesion enhancer is not particularly limited, and may include, for example: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like. These adhesion enhancers may be used alone, or in combination of two or more thereof.
Illustratively, the thermal polymerization inhibitor may include, for example: p-methoxyphenol, hydroquinone, catechol, t-butylcatechol, phenothiazine, p-methoxyphenol, and the like. These thermal polymerization inhibitors are used alone or in combination of two or more thereof.
Illustratively, the kind of the surfactant is not particularly limited, and may include, for example: a fluorine surfactant, a silicon surfactant, or a mixture thereof. These surfactants are used alone, or in combination of two or more thereof.
Illustratively, the kind of the plasticizer is not particularly limited, and may include, for example: dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerol, and the like. These plasticizers are used alone, or in combination of two or more thereof.
< color Filter and method for producing the same >
As described above, the present invention also relates to a color filter using the photosensitive resin composition and a method for manufacturing the same.
The color filter of the present invention is characterized in that a support has a colored pattern formed using the photosensitive resin composition.
Techniques for preparing RGB, BM, photo spacers, etc. by photo-curing and photolithography processes using the photosensitive resin composition are well known to those skilled in the art. Generally comprising the steps of: a step of applying a photosensitive resin composition to a support to form a photosensitive resin layer (referred to simply as a "forming step"); a step of exposing the photosensitive resin layer through a mask (referred to simply as an "exposure step"); and a step of developing the exposed photosensitive resin layer to form a colored pattern (referred to simply as "developing step").
Specifically, the photosensitive resin composition of the present invention is applied directly or via another layer onto a support (substrate) to form a photosensitive resin layer; exposing through a predetermined mask pattern to cure only the coating film irradiated with light; the color filter of the present invention is manufactured by forming a patterned film composed of pixels of each color (3 or 4 colors) by developing with a developer.
Next, each step in the production method of the present invention will be described.
Formation procedure
The photosensitive resin layer forming step is a step of applying the photosensitive resin composition of the present invention to a support to form a photosensitive resin layer.
Examples of the support to be used include soda lime glass, alkali-free glass, pyrex (pyrex) glass, quartz glass, and plastic substrate used for liquid crystal display devices and the like, as well as a support obtained by attaching a transparent conductive film to the support, a photoelectric conversion device substrate used for image pickup devices and the like, for example, a silicon substrate and the like, a Complementary Metal Oxide Semiconductor (CMOS), and the like. The substrate may be formed with a black matrix (black matrix) for isolating the pixels.
In addition, an undercoat layer may be provided on the support as needed to improve adhesion to an upper layer, prevent diffusion of a substance, or planarize the substrate surface.
As a method for applying the photosensitive resin composition of the present invention to a support, various application methods such as slit coating, an ink jet method, spin coating, roll coating, and a screen printing method can be applied.
The coating thickness of the photosensitive resin composition is preferably 0.1 to 10 μm, and more preferably 0.5 to 3 μm.
The photosensitive resin composition applied to the support is usually dried at 70 to 110 ℃ for about 2 to 4 minutes to form a photosensitive resin layer.
Exposure Process
The exposure step is to expose the photosensitive resin layer formed in the photosensitive resin layer forming step through a mask. Only the coating film portion irradiated with light is cured in this process.
The exposure is preferably performed by irradiation with radiation, and as radiation usable for the exposure, ultraviolet rays such as g-rays and i-rays are particularly preferably used, and a high-pressure mercury lamp is more preferably used. The irradiation intensity is preferably 5-1500mJ/cm 2 More preferably 10 to 500mJ/cm 2 。
Developing process
After the exposure step, an alkaline development treatment (development step) is performed to dissolve the unexposed portion in an alkaline aqueous solution in the exposure step. Thereby, only the photo-cured portion remains.
The developing temperature is usually 20 to 30 ℃ and the developing time is usually 20 to 90 seconds.
In the production method of the present invention, after the photosensitive resin layer forming step, the exposure step, and the development step are performed, a post-curing step of further curing the formed colored pattern by heating and/or exposure may be added as necessary.
The photosensitive resin layer forming step, the exposure step, and the development step (and the post-curing step added as necessary) are repeated in accordance with the desired number of tones, whereby a color filter having a desired tone composition can be produced.
The photosensitive resin composition has excellent light sensitivity, good developing property, high brightness after curing and excellent adhesion with a substrate. The manufacturing method can manufacture a high-performance color filter with high production efficiency.
Drawings
FIG. 1 is a high performance liquid chromatogram of product a1.
FIG. 2 is a high performance liquid chromatogram of T1.
FIG. 3 is a high performance liquid chromatogram of T2.
FIG. 4 is a high performance liquid chromatogram of T3.
FIG. 5 is a structural spectrum of T1 obtained by single crystal diffraction.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
1. Preparation of HABI mixed photoinitiator
1.1 preparation of HABI-based Mixed photoinitiator a1
Under the protection of nitrogen, 31.8g 2- (o-chlorophenyl) -4,5-diphenyl-imidazole (M1), 51.3g 2, 5-bis (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -imidazole (M2), 4.2g 30% caustic soda liquid, 4.0g tetrabutylammonium bromide and 300g toluene were charged into a 1L four-necked flask, heated and stirred, and 85g sodium hypochlorite (11% aqueous solution) was added dropwise at 60 to 65 ℃, followed by incubation reaction after completion of the addition, sampling was monitored by HPLC until both M1 and M2 were less than 1%, the reaction was complete, and incubation was completed. After completion of the incubation reaction, the reaction mixture was washed four times with 100g of pure water, and then the aqueous layer was extracted once with 20g of toluene, and the organic layer was distilled under reduced pressure. And adding 70g of methanol into the material obtained by distillation, heating and stirring until the solution is clear, then dropwise adding the clear solution into a solution prepared from 30g of methanol and 50g of pure water, and filtering, leaching and drying after the dropwise adding is finished to obtain 79.1g of a product a1.
The product a1 was analyzed by high performance liquid chromatography, and the results are shown in FIG. 1. The analysis result showed that the total peak content of the products of the four kinds of linking sites of 2-1', 2-3', 2'-1 and 2' -3 was 92.5%. The product a1 is a mixture of two different mono-imidazoles (i.e. M1, M2) coupled to each other and to each other, including T1, T2 and T3.
In order to accurately verify the structural composition of the product, the components T1, T2 and T3 were separately subjected to verification analysis. Pure T1, T2 and T3 are respectively obtained by means of single imidazole self-coupling, column chromatography, chromatographic separation and the like, and the structures are respectively confirmed.
FIGS. 2-4 are high performance liquid chromatograms of T1, T2, and T3, respectively.
T1 has only one peak in the liquid phase, but two peak shapes are obtained by single crystal diffraction, see figure 5. The combination of structural features can determine that the main product of the coupling of two single imidazoles is a mixture of N containing hydrogen on one imidazole and C on the 2-position on the other imidazole, thereby showing that the structure of T1 is the two connection positions of 2'-1 and 2' -3 in the invention.
The monoimidazole for synthesizing T1 is M1, belongs to symmetrical imidazole, so that 2'-1 and 2' -3 obtained by coupling have similar polarity, and liquid phase is difficult to separate. And because of the structural symmetry of M1, 2'-1 and 2-1' in the structure of the product obtained by self-coupling are the same, and 2'-3 and 2-3' are also the same, the main structure of T1 is the product of two connection sites of 2'-1 and 2' -3, namely T1-1:2,2 '-bis (o-chlorophenyl) -4,4',5,5 '-tetraphenyl-1,2' -diimidazole; t1-2:2,2 '-bis (o-chlorophenyl) -4,4',5,5 '-tetraphenyl-2', 3-diimidazole. The structural formula is as follows:
Figure BDA0002011685900000331
the single imidazole M2 for synthesizing the T2 belongs to asymmetric single imidazole, and M2 has two configurations, M2-1 and M2-2, and the structural formula is shown as follows:
Figure BDA0002011685900000332
and analyzing the pure T2 obtained by separation to obtain a main structure of four connecting position products, and performing LCMS to confirm the structure. The mass spectrometry obtains 849 and 850 molecular fragment peaks by means of instrument attached software, the molecular weight of the product is 848, the product is matched with T +1 and T +2, and the four products are proved to be similar in structure and identical in molecular weight. T2 is synthesized by asymmetric single imidazole coupling, eight main structures connected by 1-2 and 2-3 connecting positions exist theoretically, but 2'-1 and 2-1' in the structures are the same, and 2'-3 and 2-3' in the structures are also the same in the self-coupled single imidazole, so that four main structures connected by 1-2 and 2-3 connecting positions exist actually for T2, and the compositions are respectively as follows: t2-1:2,2',5,5' -tetrakis (o-chlorophenyl) -4,4 '-bis (3,4-dimethoxyphenyl) -2', 3-diimidazole; t2-2:2,2',4,5' -tetrakis (o-chlorophenyl) -4', 5-bis (3,4-dimethoxyphenyl) -1,2' -diimidazole; t2-3:2,2',5,5' -tetrakis (o-chlorophenyl) -4,4 '-bis (3,4-dimethoxyphenyl) -1,2' -diimidazole; t2-4:2,2',4,5' -tetrakis (o-chlorophenyl) -4', 5-bis (3,4-dimethoxyphenyl) -2', 3-diimidazole. The structural formula is as follows:
Figure BDA0002011685900000341
and T3 is formed by coupling M1 and M2 in pairs, the main structure of the separated pure T3 in a liquid phase is a product with four connecting positions, and LCMS confirmation is carried out on the product with the four connecting positions. The mass spectrometry obtains 755 and 756 molecular fragment peaks by means of instrument attached software, the molecular weight of the product is 754, and the product is matched with T +1 and T +2, and the four products are proved to be similar in structure and identical in molecular weight. T3 is formed by connecting symmetric imidazole M1 and asymmetric imidazole M2 pairwise, and has four main structures connected by connecting positions 1-2 and 2-3, and the main structures respectively comprise: t3-1:2,2', 5-tris (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4',5 '-diphenyl-1,2' -diimidazole; t3-2:2,2', 5-tris (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4',5 '-diphenyl-2', 3-diimidazole; t3-3:2,2', 5-tris (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4',5 '-diphenyl-2,3' -diimidazole; t3-4:2,2', 5-tris (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4',5 '-diphenyl-1', 2-diimidazole. The structural formula is as follows:
Figure BDA0002011685900000351
the product a1 is determined by combining the above experimental analysis to be T1 (T1-1, T1-2), T2 (T2-1, T2-2, T2-3, T2-4) and T3 (T3-1, T3-2, T3-3, T3-4), wherein the content of the bisimidazole compound formed by four connecting positions of 2-1', 2-3', 2'-1 and 2' -3 in a1 is 92.5%.
Referring to the above procedure, a2 to a8 were prepared, and the respective product cases are shown in the following tables 1 to 1.
TABLE 1-1
Figure BDA0002011685900000361
Note: in order to prevent the intermolecular association phenomenon, acetonitrile is used as a solvent to prepare the product with the solubility of 1 × 10 -4 measuring the ultraviolet absorption spectrum of the solution at 25 ℃ according to the formula epsilon = A/CL (molar extinction coefficient unit L × mol) -1 ×cm -1 ) The molar extinction coefficient at 365nm (i line) wavelength was calculated.
1.2 preparation of HABI type Mixed photoinitiator a9
Under the protection of nitrogen, 50g of 2- (4-chlorophenyl) -5- (6-chlorophenyl) -4- (3,4-dimethoxyphenyl) -imidazole (M3), 51g of 2, 5-bis (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -imidazole (M2), 5.6g of 30% caustic soda liquid, 4.0g of tetrabutylammonium bromide and 300g of toluene are put into a 1L four-necked flask, heated and stirred, 90g of sodium hypochlorite (11% aqueous solution) is added dropwise at 60-65 ℃, the reaction is kept warm after the dropwise addition, samples are taken and are subjected to central control by HPLC until both M2 and M3 are less than 1%, the reaction is completed, and the heat preservation is finished. After completion of the incubation reaction, the reaction mixture was washed four times with 100g of pure water, and then the aqueous layer was extracted once with 20g of toluene, and the organic layer was distilled under reduced pressure. And adding 70g of methanol into the material obtained by distillation, heating and stirring until the solution is clear, then dropwise adding the clear solution into a solution prepared from 30g of methanol and 50g of pure water, and leaching, draining and drying the material after the dropwise adding is finished to obtain 98g of a product a9.
The analysis result showed that the peak total content of the product at the four binding sites of 2-1', 2-3', 2'-1 and 2' -3 was 93.2%.
The product a9 is a mixture of two different monoimidazoles (i.e. M2, M3) coupled to each other and to each other, including T2, T4 and T5. To accurately verify the structural composition of the product, the components T2, T4 and T5 were separately subjected to verification analysis. And respectively obtaining T2, T4 and T5 by means of single imidazole self-coupling, column chromatography, chromatographic separation and the like, and respectively carrying out structure confirmation.
T2 corresponds to structure T2 in compound a1.
T4 is formed by self-coupling of asymmetric single imidazole M3, and has four main structures connected by 1-2 and 2-3 connection sites, and the main structures respectively comprise: t4-1:2,2 '-bis (4-chlorophenyl) -5,5' -bis (o-chlorophenyl) -4,4 '-bis (3,4-dimethoxyphenyl) -2,3' -diimidazole; t4-2:2,2 '-bis (4-chlorophenyl) -4,5' -bis (o-chlorophenyl) -4', 5-bis (3,4-dimethoxyphenyl) -1,2' -diimidazole; t4-3:2,2 '-bis (4-chlorophenyl) -5,5' -bis (o-chlorophenyl) -4,4 '-bis (3,4-dimethoxyphenyl) -1,2' -diimidazole; t4-4:2,2 '-bis (4-chlorophenyl) -4', 5-bis (o-chlorophenyl) -4,5 '-bis (3,4-dimethoxyphenyl) -2,3' -diimidazole. The structural formula is as follows:
Figure BDA0002011685900000381
LCMS is carried out to confirm the structure, and four structural spectrograms are consistent. The mass spectrometry obtains 849 and 850 molecular fragment peaks by means of instrument attached software, the molecular weight of the product is 848, the product is matched with T +1 and T +2, and the four product peaks are proved to be similar in structure and identical in molecular weight.
T5 is formed by coupling two by two asymmetric M2 and asymmetric M3, and four main structures connected by connecting positions 1-2 and 2-3 exist, and the main structures respectively comprise: t5-1:2- (4-chlorophenyl) -2',5,5' -tris (o-chlorophenyl) -4,4 '-bis (3,4-dimethoxyphenyl) -2,3' -diimidazole; t5-2:2'- (4-chlorophenyl) -2,5,5' -tris (o-chlorophenyl) -4,4 '-bis (3,4-dimethoxyphenyl) -1,2' -diimidazole; t5-3:2- (4-chlorophenyl) -2',5,5' -tris (o-chlorophenyl) -4,4 '-bis (3,4-dimethoxyphenyl) -2', 3-diimidazole; t5-4:2'- (4-chlorophenyl) -2,5,5' -tris (o-chlorophenyl) -4,4 '-bis (3,4-dimethoxyphenyl) -1', 2-diimidazole. The structural formula is as follows:
Figure BDA0002011685900000391
LCMS is carried out to confirm the structure, and four structural spectrograms are consistent. The mass spectrometry obtains 849 and 850 molecular fragment peaks by means of instrument attached software, the molecular weight of the product is 848, the product is matched with T +1 and T +2, and the four product peaks are proved to be similar in structure and identical in molecular weight.
The product a9 is determined by combining the above experimental analysis to be T2 (T2-1, T2-2, T2-3, T2-4), T4 (T4-1, T4-2, T4-3, T4-4) and T5 (T5-1, T5-2, T5-3, T5-4), wherein the content of the bisimidazole compound consisting of four connecting sites of 2-1', 2-3', 2'-1 and 2' -3 in a9 is 93.2%.
Referring to the above procedure, a10 to a16 were prepared separately, and the respective product cases are shown in the following tables 1 to 2.
Tables 1 to 2
Figure BDA0002011685900000392
Figure BDA0002011685900000401
Note: in order to prevent the intermolecular association phenomenon, acetonitrile is used as a solvent to prepare the product with the solubility of 1 × 10 -4 measuring the ultraviolet absorption spectrum of the solution at 25 ℃ according to the formula epsilon = A/CL (molar extinction coefficient unit L × mol) -1 ×cm -1 ) The molar extinction coefficient at 365nm (i line) wavelength was calculated.
1.3HABI Mixed photoinitiator a17
a17 is BCIM produced by Changzhou powerful new electronic materials GmbH, which contains 2-1', 2-3', 2'-1 and 2' -3 four kinds of double imidazole compounds (2-1 'and 2' -1 are the same structure and 2-3 'and 2' -3 are the same structure due to symmetrical structure), and the total mass percentage content of the four kinds of double imidazole compounds at the connection positions in A1 is 99%, and the molar extinction coefficient at 365nm (i line) wavelength is 26L x mol -1 ×cm -1 . The structural formula is as follows:
Figure BDA0002011685900000411
2. preparation of photosensitive resin composition
The photosensitive resin compositions were obtained by uniformly mixing the respective components according to the formulations shown in tables 2-1 and 2-2. Unless otherwise specified, the parts shown in the table are parts by mass.
TABLE 2-1
Figure BDA0002011685900000412
Tables 2 to 2
Figure BDA0002011685900000421
Wherein, the meanings of each component represented in tables 2-1 and 2-2 are shown in tables 2-3.
Tables 2 to 3
Figure BDA0002011685900000422
Figure BDA0002011685900000431
Referring to the above-mentioned method for measuring the molar extinction coefficient, the molar extinction coefficients of the photopolymerization initiators at a wavelength of 365nm (i-line) in examples 1 to 10 and comparative examples 1 to 12 are shown in the following tables 2 to 4.
Tables 2 to 4
Examples ε 365nm Comparative example ε 365nm
1 9683 1 10094
2 9714 2 9847
3 9742 3 9636
4 9630 4 9565
5 9661 5 9515
6 9692 6 9350
7 9947 7 9350
8 9157 8 9558
9 8367 9 9515
10 5513 10 9550
11 5733
12 11000
3. Evaluation of Performance
3.1 luminance
The photosensitive resin compositions prepared in the examples and comparative examples were coated on glass (# 1737, manufactured by corning) by a spin coating method, and then volatile components were volatilized at 100 ℃ for 3 minutes to form a photosensitive resin layer. After cooling, using ultra high pressureThe photosensitive resin layer was exposed to light with a mercury lamp at an irradiation dose of 100mJ/cm 2 . Then, the glass substrate was post-baked at 230 ℃ for 20 minutes to obtain a glass substrate having a colored layer with a film thickness of 2 μm. The chromaticity of a glass substrate having a colored layer was measured using a micro-spectrometer OSP-SP200 manufactured by Olympus (Olympus), and the Y value was measured with a C light source at a chromaticity of x =0.29 and Y = 0.59. The higher the Y value, the better the performance as a color filter for a liquid crystal display device.
The Y value is determined according to the following criteria:
o: the Y value is 57 or more;
very good: the Y value is 55 or more and less than 57;
● : the value of Y is less than 55.
3.2 light sensitivity
The photosensitive resin compositions prepared in the examples and comparative examples were coated on glass (# 1737, manufactured by corning) by a spin coating method, and then volatile components were volatilized at 100 ℃ for 3 minutes to form a photosensitive resin layer. After cooling, the projection exposure apparatus was reduced to a wavelength of 365nm by using an i-line reduction projection exposure apparatus, and the exposure was adjusted to 50mJ/cm by passing through a mask 20 μm in the vertical direction by 20 μm in the horizontal direction 2 The coating film was irradiated in the manner described above. After the irradiation, the coating film was developed at 23 ℃ for 60 seconds using a developing solution (trade name: CD-2000, 60%, manufactured by Fuji film electronics). Subsequently, the image was rinsed with running water for 20 seconds, and then spray-dried to obtain a pattern image. Image formation was confirmed by an optical microscope. The pixel pattern obtained has a large width, and is therefore highly sensitive and thus preferable. The width of the obtained pixel pattern is determined by the following criteria:
o: more than 35 μm;
very good: 20 μm or more and less than 35 μm;
● : less than 20 μm.
3.3 developability
For the photosensitive resin compositions prepared in each of examples and comparative examples, the liquid composition was applied to a glass substrate using a spin coaterThen, the resultant was dried at 100 ℃ for 5min to remove the solvent, thereby forming a coating film having a film thickness of 10 μm; in order to obtain a coating film with the thickness, the coating process can be completed once or carried out for multiple times; cooling the substrate with the coating film to room temperature, attaching a mask plate, passing through RW-UV.70201 crawler-type exposure machine equipped with high-pressure mercury lamp, irradiating wavelength of 250-450nm, and receiving energy of 80mJ/cm 2 Exposing the coating film under ultraviolet irradiation through the gaps of the mask plate; developing with 1% NaOH aqueous solution at 25 deg.C, washing with ultrapure water, and air drying; and finally, post-baking for 30min in a baking oven at 240 ℃ to obtain the pattern transferred by the mask plate.
The pattern on the substrate was observed with a Scanning Electron Microscope (SEM) to evaluate developability. The criteria for determination are as follows:
o: no residue was observed in the unexposed parts;
very good: a small amount of residue was observed in the unexposed parts, but the residual amount was acceptable;
● : a clear residue was observed in the unexposed parts.
3.4 evaluation of adhesion
With the pattern obtained in 3.3 as an object, the adhesion of the coating film is evaluated by a cross-cut experimental method with reference to GB9286-88 cross-cut test of paint films of colored paint and varnish. The grade is 0-5 (6 grades in total) according to the damage degree, wherein the grade is 0, and no small lattice falls off from the film surface; grade 5 was very poor and severe flaking occurred on the membrane surface.
The evaluation results are shown in table 3.
TABLE 3
Figure BDA0002011685900000461
Figure BDA0002011685900000471
As can be seen from the results in table 3, the compositions of the examples exhibited excellent sensitivity and good developability, high brightness after curing, and excellent adhesion to the substrate when applied to the preparation of an optical filter. The comprehensive application performance advantage of the invention is remarkable compared with the photosensitive resin composition of the comparative example.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.

Claims (16)

1. A photosensitive resin composition for a color filter, comprising the following components:
(A) A photopolymerization initiator comprising a photopolymerization initiator A1 and at least one oxime ester photoinitiator A2;
(B) An alkali soluble resin;
(C) A compound having at least one polymerizable unsaturated bond;
(D) A colorant;
(E) A hydrogen donor;
wherein the photopolymerization initiator A1 is a hexaarylbisimidazole mixed photoinitiator which is formed by coupling two different triarylimidazoles and has a structure shown in a general formula (I), wherein the hexaarylbisimidazole mixed photoinitiator contains four kinds of bisimidazole compounds of 2-1', 2-3', 2'-1 and 2' -3 connecting positions, and the total mass percentage content of the four kinds of bisimidazole compounds of the connecting positions in the photopolymerization initiator A1 is more than 92 percent,
Figure FDA0003808591370000011
in the general formula (I), ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Each independently represents a substituted or unsubstituted aryl group;
the aryl group is phenyl;
the substituent on the aryl is halogen, nitro, C 1 -C 8 Alkoxy group of (a);
and the photopolymerization initiator (A) has a molar extinction coefficient at i-line (365 nm) of 5000-10000.
2. The composition of claim 1, wherein: the mass ratio of the photopolymerization initiator A1 to the oxime ester photoinitiator A2 in the composition is 1:5-5:5.
3. The composition of claim 1, wherein: the substituents on the aryl are chlorine, nitro and C 1 -C 5 Alkoxy group of (2).
4. The composition according to any one of claims 1-3, characterized in that: ar (Ar) 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 At least one of which is an aryl group having a halogen substituent.
5. The composition of claim 4, wherein: the halogen substituent is chlorine.
6. The composition according to any one of claims 1-3, characterized in that: as the photopolymerization initiator A1, the total mass percentage content of the bisimidazole compounds satisfying four linking sites of 2-1', 2-3', 2'-1 and 2' -3 of the structure shown in the general formula (I) is more than 95%.
7. The composition of claim 6, wherein: the photopolymerization initiator A1 is composed of a bisimidazole compound having four kinds of linking sites of 2-1', 2-3', 2'-1 and 2' -3 satisfying the structure represented by the general formula (I).
8. The composition of claim 1, wherein: the alkali-soluble resin (B) is an alkali-soluble resin of a carboxyl group-containing copolymer.
9. The composition of claim 8, wherein: the alkali-soluble resin (B) is a copolymer of an ethylenically unsaturated monomer having a carboxyl group and other copolymerizable ethylenically unsaturated monomer.
10. The composition of claim 1, wherein: the compound (C) having at least one polymerizable unsaturated bond is at least one selected from the group consisting of acrylate compounds and methacrylate compounds.
11. The composition of claim 1, wherein: the colorant (D) is selected from pigments and/or dyes.
12. The composition of claim 1, wherein: the hydrogen donor (E) is at least one of an amine compound, a carboxylic acid compound, a mercapto group-containing organic sulfur compound, and an alcohol compound.
13. A photosensitive resin composition for a color filter, comprising the following components:
(A) A photopolymerization initiator comprising a photopolymerization initiator A1 and at least one oxime ester photoinitiator A2;
(B) An alkali soluble resin;
(C) A compound having at least one polymerizable unsaturated bond;
(D) A colorant;
(E) A hydrogen donor;
wherein the photopolymerization initiator A1 is a hexaarylbisimidazole mixed photoinitiator and has a structure shown as a general formula (I), wherein the photopolymerization initiator A1 contains four kinds of bisimidazole compounds of 2-1', 2-3', 2'-1 and 2' -3 connecting positions, and the total mass percentage content of the four kinds of bisimidazole compounds of connecting positions in the photopolymerization initiator A1 is more than 92 percent,
Figure FDA0003808591370000031
in the general formula (I), ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Each independently represents a substituted or unsubstituted aryl group;
the aryl group is phenyl;
the substituent on the aryl is halogen, nitryl and C 1 -C 8 Alkoxy group of (a);
and the photopolymerization initiator (A) has a molar extinction coefficient at i-line (365 nm) of 5000-10000;
and, the photopolymerization initiator A1 contains at least one of the following combinations corresponding to the bisimidazole compounds of the four linking sites of 2-1', 2-3', 2'-1 and 2' -3:
A1-2：
Figure FDA0003808591370000041
A1-3：
Figure FDA0003808591370000042
Figure FDA0003808591370000051
A1-4：
Figure FDA0003808591370000052
A1-5：
Figure FDA0003808591370000053
A1-6：
Figure FDA0003808591370000054
Figure FDA0003808591370000061
A1-7：
Figure FDA0003808591370000062
14. a color filter, characterized in that: a support having thereon a colored pattern formed using the photosensitive resin composition according to any one of claims 1 to 13.
15. The manufacturing method of the color filter comprises the following steps: a step of forming a photosensitive resin layer by applying the photosensitive resin composition according to any one of claims 1 to 13 on a support; exposing the photosensitive resin layer through a mask; and a step of forming a colored pattern by developing the exposed photosensitive resin layer.
16. The manufacturing method according to claim 15, characterized in that: further comprises a post-curing step of further curing the formed colored pattern by heating and/or exposure.
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