CN111752096A - 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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Publication number
CN111752096A
CN111752096A CN201910248409.8A CN201910248409A CN111752096A CN 111752096 A CN111752096 A CN 111752096A CN 201910248409 A CN201910248409 A CN 201910248409A CN 111752096 A CN111752096 A CN 111752096A
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acid
photosensitive resin
bis
compound
composition
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CN111752096B (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 Green Photosensitive Materials Co ltd
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Priority to PCT/CN2020/081284 priority patent/WO2020200018A1/en
Priority to JP2021557998A priority patent/JP7242100B2/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
    • 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
    • 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)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Optical Filters (AREA)
  • Photosensitive Polymer And Photoresist Processing (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 method in industry, and a color filter is formed by coating a photosensitive resin composition containing a colorant on a transparent substrate, then performing 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 in photosensitive resin compositions is still the main means for obtaining products with better 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) photopolymerization initiators including a photopolymerization initiator a1 and at least one oxime ester photoinitiator a 2;
(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), Ar1、Ar2、Ar3、Ar4、Ar5、Ar6May be the same or different and each independently represents a substituted or unsubstituted aryl group;
and the molar extinction coefficient of the photopolymerization initiator (A) at the i line (365nm) is between 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 linking sites, and the total mass percentage content of the four kinds of double imidazole compounds of linking sites in the photopolymerization initiator A1 is more than 92%,
Figure BDA0002011685900000031
in the general formula (I), Ar1、Ar2、Ar3、Ar4、Ar5、Ar6May be the same or different and each independently represents a substituted or unsubstituted aryl group;
and the molar extinction coefficient of the photopolymerization initiator (A) at the i line (365nm) is between 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, C1-C20Alkyl or alkenyl of, C1-C8Wherein 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, C1-C10Alkyl or alkenyl of, C1-C5Wherein the methylene group in each independent variable may be optionally substituted with oxygen, sulfur, or an imine group.
Further preferably, Ar1、Ar2、Ar3、Ar4、Ar5、Ar6At 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 stereoscopic 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 exposed regions 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 the photopolymerization initiator a1 having the above-mentioned definition 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 performance than that of the photopolymerization initiator A1, and if the total content of these four linking sites is less than 92%, the performance tends to be significantly deteriorated.
The photopolymerization initiator a1 used in the present invention is preferably a bisimidazole compound having four linking sites of 2-1 ', 2-3', 2 '-1 and 2' -3 satisfying the structure represented by the general formula (I) in which the total content by mass is 95% or more, and particularly preferably a bisimidazole compound having four linking sites of 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 (365nm) is between 5000-10000, the photopolymerization initiator has suitable sensitivity, does not reduce the curing speed due to insufficient sensitivity, and does not cause undercut due to excessively high sensitivity.
The HABI type photoinitiators are well known in the art of photoresists and may be prepared by oxidative coupling of triarylimidazoles or substituted triarylimidazoles, as described in the prior art, for example, in US3784557, US4622286 and US4311783 (the entire contents of which are incorporated herein by reference). The photopolymerization initiator A1 meeting the composition requirements of the invention can be conveniently obtained by adding a solvent recrystallization process on the basis of the prior art. 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 No. 201811451262.4 (which is incorporated herein by reference in its entirety).
Illustratively, the photopolymerization initiator a1 corresponding to the bisimidazole compounds at 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 a 1.
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 oxime lipid photoinitiators or adding other types of photoinitiators (such as acetophenone compounds, triazine compounds and the like), the method for introducing the oxime lipid photoinitiators in the presence of the photopolymerization initiator A1 can obviously improve the sensitivity and the developability of the composition, and is also beneficial to 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-benzoxy-ate, 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-keto-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) - (3-cyclohexyl) -propane-1, 2-dione-2-cyclohexanecarboxylic acid oxime ester, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] - (3-cyclopentyl) -propane-1, 2-dione-2-oxime acetate, 1- (6-o-methylbenzoyl-9-ethylcarbazole-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-ethylcarbazole-3-yl) - (3-cyclopentylacetone) -1-oxime cyclohexanecarboxylate, 1- (4-benzoyldiphenyl sulfide) -3-cyclopentylacetone) -1-oxime cyclohexanecarboxylate, 1- (6-o-methylbenzoyl-9-ethylcarbazole-3-yl) -one-oxime (3-cyclopentyl) -propane-1, 2-dione-2-o-methylbenzoic acid oxime ester, 1- (4-thiophenylphenyl) - (3-cyclopentyl) -propane-1, 2-dione-2-cyclohexanecarboxylic acid oxime ester, 1- (4-thenoyl-diphenylsulfide-4' -yl) -3-cyclopentyl-propane-1-one-acetic acid oxime ester, 1- (4-benzoyldiphenylsulfide) - (3-cyclopentyl) -propane-1, 2-dione-2-oxime acetate, 1- (6-nitro-9-ethylcarbazol-3-yl) -3-cyclohexyl-propane-1-one-acetic acid oxime ester, and salts thereof, 1- (6-o-methylbenzoyl-9-ethylcarbazol-3-yl) -3-cyclohexyl-propan-1-one-oxime acetate, 1- (6-thenoyl-9-ethylcarbazol-3-yl) - (3-cyclohexylacetone) -1-oxime acetate, 1- (6-furfurylcarbazol-9-ethylcarbazol-3-yl) - (3-cyclopentylacetone) -1-oxime acetate, 1, 4-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-furoyl-9-ethylcarbazol-3-yl) - (3-cyclohexylacetone) -1-oxime acetate, 1- (4-phenylthiophenyl) - (3-cyclohexyl) -propane-1, 2-dione-3-oxime benzoate, 1- (6-thenoyl-9-ethylcarbazol-3-yl) - (3-cyclohexyl) -propane-1, 2-dione-2-oxime acetate, oxime, 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-propan-1-one-oxime acetate, 1- {4- [4- (thiophene-2-formyl) phenylthiophenyl ] phenyl } -3-cyclopentylpropan-1, 2-dione-2-oxime acetate, and pharmaceutically acceptable salts thereof, 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-methylphenyl) methanone-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -3-cyclopentyl-propane-1-one-oxime benzoate, methyl acetate, ethyl acetate, 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-carbethoxyoxime ester, and the like. These oxime ester compounds may be used alone or in combination of two or more.
Based on the consideration 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, α -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.
Examples of the copolymerizable unsaturated monomer (Q) include 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 monoacryloyl group or a monomethacryloyl group at the end 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 A copolymer of a monomer, a copolymer of (meth) acrylic acid/(meth) acrylic acid-2-hydroxyethyl ester/(meth) acrylic acid benzyl ester/polymethyl methacrylate macromonomer, a copolymer of methacrylic acid/styrene/(meth) acrylic acid benzyl ester/N-phenylmaleimide, a copolymer of (meth) acrylic acid/succinic acid mono [2- (meth) acryloyloxyethyl ] ester/styrene/(meth) acrylic acid allyl ester/N-phenylmaleimide, a copolymer of (meth) acrylic acid/styrene/(meth) acrylic acid benzyl ester/glycerol mono (meth) acrylic ester/N- A phenylmaleimide copolymer, a (meth) acrylic acid/ω -carboxypolycaprolactone mono (meth) acrylate/styrene/(meth) acrylic acid benzyl ester/glycerol mono (meth) acrylate/N-phenylmaleimide copolymer, 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 (polystyrene equivalent value measured by GPC method) of 1000-.
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 drawback that the light-shielding property 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, methyl acrylate, ethyl acrylate, decyl acrylate, dodecyl acrylate, isobutyl acrylate, dodecyl acrylate, 2,2, 2-trifluoroethyl acrylate, 1, 3-butanediol methyl ether acrylate, butoxyethyl acrylate, beta-carboxyethyl acrylate, monoacryloxyethyl 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, EO-modified tetrabromobisphenol A diacrylate, bisphenol A diacrylate, 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: methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, methyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, n-butyl methacrylate, n-, 2,2, 2-trifluoroethyl methacrylate, 2,2,3, 3-tetrafluoropropyl methacrylate, 1H-hexafluoroisopropyl methacrylate, 2-methoxyethyl methacrylate, 1, 3-butanediol methyl ether methacrylate, butoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol #400 methacrylate, methoxypropylene glycol methacrylate, ethoxydiethylene glycol methacrylate, 2-ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, pentaerythritol penta (meth) acrylate, poly, Dipentaerythritol hexamethacrylate, and the like.
Examples of the compound (C) having at least one polymerizable unsaturated bond include, but are not limited to, 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, vinyl 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 the 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) in the present invention is not particularly limited, 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, dianthraquinone-based pigments, anthrapyrimidine 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, the 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(15:3, 15:4, 15:6, 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 15:3, 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 of both 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, etc.; blue dyes 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, there 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, 247, 244, 245, 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, 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, etc.; 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 '-bis (dimethylamino) benzophenone, 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 and the like.
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), Aliphatic secondary polyfunctional thiol compounds such as diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), dipentaerythritol hexa (3-mercaptovalerate), and the like; 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-propanetriol, 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 auxiliary agents 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 ', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4 ', 5 ' -diphenyl-1, 1 ' -diimidazole, 2 ', 5-tris (2-fluorophenyl) -4- (3, 4-dimethoxyphenyl) -4 ', 5 ' -diphenyl-diimidazole, 2 ' -bis (2, 4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-diimidazole, 2 ' -bis (2-fluorophenyl) -4- (o-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4 ', 5 ' -diphenyl-diimidazole, 2 ' -bis (2-fluorophenyl) -4,4 ', 5,5 ' -tetraphenyl-diimidazole, 2 ' -bis (2-methoxyphenyl) -4,4 ', 5,5 ' -tetraphenyl-diimidazole, 2 ' -bis (2-chloro-5-nitrophenyl) -4,4 ' -bis (3, 4-dimethoxyphenyl) -5,5 ' -bis (o-chlorophenyl) -diimidazole, 2 ' -bis (2-chloro-5-nitrophenyl) -4- (3, 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' -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, methyl-ethyl-2, 4-bis (trichloromethyl) -s-triazin, 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 } propanamide, benzyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid, and the like, 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' -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 coumarins 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-ethylaccridine, 9- (4-bromophenyl) acridine, 9- (3-chlorophenyl) acridine, 1, 7-bis (9-acridine) heptane, 1, 5-bis (9-acridinopentane), 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-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4 '-methylbenzophenone sulfide, 4-benzoyl-4' -ethyldiphenyl sulfide, 4-benzoyl-4 '-propyldiphenyl sulfide, 4' -bis (diethylamino) benzophenone, 4-p-tolylmercapto benzophenone, 2,4, 6-trimethylbenzophenone, 4-methylbenzophenone, 4 '-bis (dimethylamino) benzophenone, 4' -bis (methyl, ethylamino) benzophenone, acetophenone dimethyl ketal, benzophenone derivatives, and mixtures thereof, Benzil dimethyl ketal,. alpha. '-dimethylbenzyl ketal,. alpha.' -diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-p-hydroxyethyl etherylphenylacetone, 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-ethylanthraquinone-9, 10-diethyl ester, 1,2, 3-trimethylanthracene-9, 10-dioctyl ester, 2-ethylanthrane-9, 10-bis (methyl chlorobutyrate), 2- {3- [ (3-ethyloxetan-3-yl) methoxy ] -3-oxopropyl } anthracene-9, 10-diethyl ester, 9, 10-dibutoxyanthracene, 9, 10-diethoxy-2-ethylanthrane, 9, 10-bis (3-chloropropoxy) anthracene, 9, 10-bis (2-hydroxyethylmercapto) anthracene, 2-methylanthraquinone, 2, 3-dimethylanthraquinone, 2-ethylanthraquinone, 10-, 9, 10-bis (3-hydroxy-1-propylmercapto) anthracene and the like. 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), methoxybutyl acetate (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, 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-cyclohexen-1-one), diisobutyl ketone (2, 6-dimethyl-4-heptanone), N-methylpyrrolidone (4-methylaminolactam or NMP), methanol, ethanol, isopropanol, N-propanol, 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; aliphatic tricarboxylic acids such as 1,2, 3-propanetricarboxylic acid, aconitic acid, norbornanetricarboxylic 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-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, N- (2-methoxyethoxy) -3-aminopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, vinyltrimethoxysilane, 3, 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 "forming step"); a step of exposing the photosensitive resin layer through a mask (referred to simply as "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 explained.
Formation process
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 suitable supports include soda lime glass, alkali-free glass, pyrex (pyrex) glass, quartz glass, and plastic substrates used for liquid crystal display devices and the like, supports obtained by attaching a transparent conductive film to the supports, photoelectric conversion device substrates used for image sensors and the like, such as silicon substrates and the like, Complementary Metal Oxide Semiconductor (CMOS), and the like. The substrate may be formed with a black matrix (black matrix) for isolating each pixel.
In addition, a lower coating 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/cm2More preferably 10 to 500mJ/cm2。
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 sensitivity, good developability, 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 a 1.
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
31.8g of 2- (o-chlorophenyl) -4, 5-diphenyl-imidazole (M1), 51.3g of 2, 5-bis (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -imidazole (M2), 4.2g of 30% caustic soda liquid, 4.0g of tetrabutylammonium bromide and 300g of toluene are put into a 1L four-neck flask under the protection of nitrogen, heated and stirred, 85g of sodium hypochlorite (11% aqueous solution) is added dropwise at 60-65 ℃, the reaction is kept warm after the addition is finished, samples are taken and are controlled by HPLC until both M1 and M2 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 filtering, leaching and drying after the dropwise adding is finished to obtain 79.1g of a product a 1.
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 product at the four binding 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.M 1, M2) coupled to each other and to each other, including T1, T2 and T3.
To accurately verify the structural composition of the product, the compositions 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 were obtained by single crystal diffraction, see FIG. 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 of the other imidazole, thereby indicating that the structure of T1 is the two connection positions of 2 '-1 and 2' -3 in the invention.
The monoimidazole synthesized by T1 is M1, belongs to symmetrical imidazole, so that 2 '-1 and 2' -3 obtained by coupling have similar polarities, and the 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, so that the main structure of T1 is a 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 synthesized by T2 belongs to asymmetric single imidazole, and M2 exists in two configurations, M2-1 and M2-2, and the structural formula is shown as follows:
Figure BDA0002011685900000332
the isolated pure T2 was analyzed for four linker products and LCMS confirmed 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, there are eight main structures connected by 1-2 and 2-3 connection sites theoretically, but for self-coupled single imidazole, 2 '-1 and 2-1' in the structure are the same, and 2 '-3 and 2-3' are also the same, so for T2, there are four main structures connected by 1-2 and 2-3 connection sites actually, and their compositions are: 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
the 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 the LCMS is carried out on the product with the four connecting positions to confirm the structure. 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, has four main structures connected by connecting positions 1-2 and 2-3, and comprises the following components: 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 T1(T1-1, T1-2), T2(T2-1, T2-2, T2-3, T2-4) and T3(T3-1, T3-2, T3-3 and T3-4) by combining the above experimental analysis, wherein the content of the bisimidazole compound consisting of four connecting positions of 2-1 ', 2-3', 2 '-1 and 2' -3 in the a1 is 92.5 percent.
Referring to the above procedure, a2-a8 was prepared, each product case being shown in Table 1-1 below.
TABLE 1-1
Figure BDA0002011685900000361
Note that in order to prevent the intermolecular association phenomenon, acetonitrile is used as a solvent to prepare the product with the solubility of 1 × 10-4measuring the ultraviolet absorption spectrum of the solution at 25 ℃, and then obtaining the product according to the formula of 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-based Mixed photoinitiator a9
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, 4.0g of tetrabutylammonium bromide and 300g of toluene were put into a 1L four-necked flask under nitrogen protection, heated and stirred, and 90g of an 11% aqueous solution was added dropwise at 60 to 65 ℃ followed by incubation after completion of the addition, sampling was subjected to central control by HPLC until both M2 and M3 became 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 leaching, draining and drying the material after the dropwise adding is finished to obtain 98g of a product a 9.
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 mono-imidazoles (i.e.M 2, M3) coupled to each other and to each other, including T2, T4 and T5. To accurately verify the structural composition of the product, the compositions T2, T4, and T5 were separately subjected to verification analysis. The structures of T2, T4 and T5 are respectively obtained by means of single imidazole self-coupling, column chromatography, chromatographic separation and the like, and the structures are respectively confirmed.
T2 is identical with structure T2 in compound a 1.
T4 is formed by self-coupling asymmetric single imidazole M3, and has four main structures connected by 1-2 and 2-3 connecting positions, and the compositions of the main structures are respectively as follows: 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, there are four main structures connected by 1-2 and 2-3 connection sites, and the compositions are respectively: 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 positions of 2-1 ', 2-3', 2 '-1 and 2' -3 in a9 is 93.2%.
With reference to the above procedure, a10-a16 was prepared separately, each product case being shown in tables 1-2 below.
Tables 1 to 2
Figure BDA0002011685900000392
Figure BDA0002011685900000401
Note that in order to prevent the intermolecular association phenomenon, acetonitrile is used as a solvent to prepare the product with the solubility of 1 × 10-4measuring the ultraviolet absorption spectrum of the solution at 25 ℃, and then obtaining the product according to the formula of 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
a17Is BCIM produced by Changzhou powerful new electronic material GmbH, wherein the BCIM contains 2-1 ', 2-3', 2 '-1 and 2' -3 four kinds of double imidazole compounds (because of the symmetrical structure, 2-1 'and 2' -1 are the same structure, 2-3 'and 2' -3 are the same structure), and the total mass percentage content of the four kinds of double imidazole compounds at the connecting positions in A1 is 99%, and the molar extinction coefficient at the wavelength of 365nm (i line) is 26L × 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 ε365nm Comparative example ε365nm
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, the photosensitive resin layer was exposed to light using an ultrahigh pressure mercury lamp with an irradiation light amount of 100mJ/cm2. 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 Y0.59. 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 applied to glass (#1737, manufactured by Corning Inc.) by spin coating, and then the volatile components were volatilized at 100 ℃ for 3 minutes to form a photosensitive resin layer, after cooling, the photosensitive resin layer was passed through a mask 20 μm in length and 20 μm in length × by an i-line reduction projection exposure apparatus at a wavelength of 365nm and an exposure amount of 50mJ/cm2The coating film was irradiated. 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). Then, 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 coated on a glass substrate using a spin coater, and then dried at 100 ℃ for 5min to remove the solvent, to form 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 a RW-UV 70201 crawler-type exposure machine equipped with a high-pressure mercury lamp, irradiating at a wavelength of 250-450nm, and receiving energy at a single exposure of about 80mJ/cm2Exposing 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 present invention is significant compared to 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 changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (14)

1. A photosensitive resin composition for a color filter, comprising the following components:
(A) photopolymerization initiators including a photopolymerization initiator a1 and at least one oxime ester photoinitiator a 2;
(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 in a general formula (I), wherein the photopolymerization initiator A1 contains four bisimidazole compounds with 2-1 ', 2-3', 2 '-1 and 2' -3 connecting positions, the total mass percentage content of the four bisimidazole compounds with the connecting positions in A1 is more than 92%,
Figure FDA0002011685890000011
in the general formula (I), Ar1、Ar2、Ar3、Ar4、Ar5、Ar6May be the same or different and each independently represents a substituted or unsubstituted aryl group;
and the molar extinction coefficient of the photopolymerization initiator (A) at the i line (365nm) is between 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: ar (Ar)1、Ar2、Ar3、Ar4、Ar5、Ar6Which may be the same or different, each independently represents a substituted or unsubstituted aryl group, and the aryl group is a phenyl group.
4. The composition according to any one of claims 1-3, characterized in that: the substituent on the aryl is halogen, nitryl, cyano, amino, hydroxyl and C1-C20Alkyl or alkenyl of, C1-C8Wherein the methylene group in each independent variable (i.e., each substituent) may be optionally substituted with oxygen, sulfur, an imine group.
5. The composition according to any one of claims 1-3, characterized in that: the substituent on the aryl is fluorine, chlorine, bromine, nitro, cyano, amino, hydroxyl, C1-C10Alkyl or alkenyl of, C1-C5Wherein the methylene group in each independent variable may be optionally substituted with oxygen, sulfur, or an imine group.
6. The composition according to any one of claims 1-3, characterized in that: ar (Ar)1、Ar2、Ar3、Ar4、Ar5、Ar6At least one is an aryl group having a halogen substituent; preferably, the halogen substituent is chlorine.
7. The composition according to any one of claims 1-3, characterized in that: the photopolymerization initiator A1 is preferably composed of a bisimidazole compound having four linking sites of 2-1 ', 2-3', 2 '-1 and 2' -3, satisfying the structure represented by the general formula (I), in which the total content by mass of the bisimidazole compound is 95% or more, and preferably composed of a bisimidazole compound having four 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, preferably a copolymer of an ethylenically unsaturated monomer having a carboxyl group and another copolymerizable ethylenically unsaturated monomer.
9. 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.
10. The composition of claim 1, wherein: the colorant (D) is selected from pigments and/or dyes.
11. 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.
12. 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 11.
13. 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 11 on a support; exposing the photosensitive resin layer through a mask; and a step of developing the exposed photosensitive resin layer to form a colored pattern.
14. The manufacturing method according to claim 13, 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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