CN111234094B - Modified dye, photosensitive resin composition containing same and application - Google Patents
Modified dye, photosensitive resin composition containing same and application Download PDFInfo
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- CN111234094B CN111234094B CN201811437247.4A CN201811437247A CN111234094B CN 111234094 B CN111234094 B CN 111234094B CN 201811437247 A CN201811437247 A CN 201811437247A CN 111234094 B CN111234094 B CN 111234094B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B68/00—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- 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
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Abstract
The invention discloses a modified dye, a photosensitive resin composition containing the same and application thereof, wherein the modified dye comprises at least one structural unit (A), at least one structural unit (B), at least one structural unit (C) and at least one structural unit (D); the photosensitive resin composition comprises 3.1-15% of the modified dye, 2-10% of a monomer, 1-5% of an alkali-soluble resin, 0.1-1% of an initiator and 100% of a solvent; the photosensitive resin composition is used for a liquid crystal panel, particularly an optical filter of the liquid crystal panel. The modified dye provided by the invention has good heat resistance and good dispersibility in the resin composition, so that the resin composition has good heat resistance, stability and developability at the same time.
Description
Technical Field
The invention relates to the technical field of photoetching, in particular to a modified dye, a photosensitive resin composition containing the modified dye and application of the photosensitive resin composition.
Background
The color photoresist is a key raw material for preparing the optical filter of the liquid crystal panel, the color rendering performance of the liquid crystal panel is determined to a certain extent, and with the continuous development of display technology, the liquid crystal panel puts higher requirements on performance indexes such as brightness, power consumption and the like, so that the light transmittance of the color photoresist needs to be continuously improved. Most of color photoresists in the prior art are pigment-type, the pigment has good heat resistance and stable performance, but the light transmittance is low, so that the requirements of technical development cannot be met gradually, in recent years, the pigment is continuously replaced by dye in high-end display equipment, and the dye-type color filter becomes the development trend of the future filter technology. The dye has higher light transmittance than the pigment type, but the dye tends to have a problem of poor heat resistance.
CN108508700A discloses a dye monomer and a color photoresist, where the dye monomer is applied to the preparation of a color photoresist, and a first monomer group containing at least one preset functional group is connected to a molecule of the dye monomer through a chemical bond, and the preset functional group undergoes a polymerization reaction with an adjacent dye monomer molecule in the curing process of the color photoresist to form a dye cross-linked network for fixing the dye monomer in the color photoresist. The problems that dye molecules diffuse along with thermal movement to pollute adjacent film layers or pixels or cause flooding due to dye precipitation and the like are solved, but the heat resistance is poor.
CN108170001A discloses a photoresist composition, a color filter and a display panel. The photoresist composition includes: colorants, alkali-soluble resins, reactive monomers, photo initiators, solvents and additives; wherein the colorant comprises a yellow dye, the solution can reduce the light scattering of the photoresist composition and improve the tinting strength of the photoresist composition by adding the yellow dye having a specific chemical formula to the photoresist composition. The yellow dye is used for preparing a photoresist composition, and a color filter and a display panel are further prepared by the photoresist composition so as to improve the color display effect of the color filter and the display panel, but the heat resistance of the photoresist is poor.
CN107168012A discloses a color photoresist and a preparation method thereof. The color photoresist is prepared by adding a certain amount of fluorescence quencher into a composition containing dye; the preparation method comprises the following steps: (1) dissolving alkali-soluble resin and a monomer in a part of a solvent to obtain a mixture A; (2) dissolving the photoinitiator in the remaining solvent to obtain a mixture B; (3) mixing the mixture A, the mixture B, the additive and the fluorescence quenching agent to obtain a mixture C; (4) and mixing the mixture C, the pigment dispersion liquid and the dye to obtain the color photoresist. The color photoresist reduces the fluorescence effect of the dye and improves the contrast of the color photoresist because a certain amount of fluorescence quenching agent is added into the dye-containing composition, thereby improving the picture quality, but the heat resistance of the photoresist is not improved yet.
Therefore, there is a need in the art to develop a dye that not only can be well dispersed in a photoresist composition, but also can provide a photoresist composition including the dye with excellent heat resistance and developability.
Disclosure of Invention
The invention aims to provide a modified dye, which comprises at least one structural unit (A), at least one structural unit (B), at least one structural unit (C) and at least one structural unit (D);
said X is—Selected from dye anions having sulfonic acid groups—SO3Dye or Dye anions carrying carboxyl groups—OOC-Dye; wherein "Dye" is a Dye.
The R is1、R2And R4Each independently selected from methyl or hydrogen;
the R is3Any one selected from hydrocarbyl or oxygenated group-substituted hydrocarbyl;
the R is5Any one selected from hydrogen, benzyl and C1-C12 alkyl;
the number of the structural units (A) is n1The total number of structural units in the modified dye is n;
n is1The/n is any value of 0.05 to 0.6, such as 0.06, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.58, and the like;
the weight average molecular weight of the modified dye is 5000-10000, such as 5200, 5500, 5800, 6000, 6500, 6800, 7000, 7500, 8000, 8500, 9000, 9500, 9800 and the like.
The modified dye is formed by connecting a quaternized polymer and a small molecule dye with sulfonic acid group or carboxyl group, and the polymer has better heat resistance, so the large molecule dye also has good heat resistance, and the modified dye can be stably dispersed in the photosensitive resin composition.
In addition, the modified dye may be a polymer linked to a small molecule dye, a polymer linked to at least two small molecule dyes, at least two polymers linked to a small molecule dye, or a plurality of polymers linked to a plurality of small molecule dyes, which is not limited in the present invention.
The structural unit (A) is connected with the micromolecular dye through the action of electric charges, so that the dye has excellent dispersion stability in the photosensitive resin composition, the structural unit (B) enables the modified dye to have excellent heat resistance and further improves the dispersion stability of the modified dye in the photosensitive resin composition, the structural unit (C) can improve the compatibility of the modified dye and the photosensitive resin composition and further improves the dispersion stability, and the structural unit (D) is beneficial to improving the developing property of the photosensitive resin composition containing the modified dye. The structural units (A), (B), (C) and (D) are matched with each other to realize synergistic interaction, so that the modified dye is further optimized in dispersibility, heat resistance and developability.
The positive charge of the structural unit (A) of the modified dye may be obtained by acidification or quaternization, when obtained by acidification, R5Is hydrogen, when obtained by quaternization, R5Is benzyl or alkyl.
When n is1When the value of/n is any of 0.05 to 0.6, stable dispersion of the modified dye in the photosensitive resin composition is more facilitated, and a certain adverse effect is generated when the specific gravity of the structural unit (A) is too high or too low.
Preferably, said n is1The value of/n is 0.1 to 0.3, for example, 0.15, 0.2, 0.25, etc.
Preferably, theThe number of the structural units (B) is n2N is said to2The/n is any value of 0.1 to 0.8, for example, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.78, etc.
Preferably, said n2The/n is any value of 0.2 to 0.6, for example, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, etc.
Preferably, the number of the structural units (C) is n3N is said to3The/n is any value of 0.1 to 0.7, for example, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, etc.
Preferably, said n3The value of/n is 0.2 to 0.5, for example, 0.25, 0.3, 0.35, 0.4, 0.45, etc.
Preferably, the number of the structural units (D) is n4N is said n4The value of/n is 0.05 to 0.6, for example, 0.06, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.58, etc.
Preferably, said n4The value of/n is 0.1 to 0.3, for example, 0.15, 0.2, 0.25, etc.
Preferably, said n2The value of/n is 0.1-0.8, wherein n3The value of/n is 0.1-0.7, wherein n4The value of/n is 0.05 to 0.6.
Preferably, said n1The value of/n is 0.1-0.3, wherein n2The value of/n is 0.2-0.6, wherein n3The value of/n is 0.2-0.5, wherein n4The value of/n is 0.1 to 0.3.
Preferably, said R is3Selected from C1-C12 hydrocarbon groups.
Preferably, said R is3And any one selected from the group consisting of methyl, ethyl, n-butyl, isobutyl, tert-butyl, n-dodecyl, 2-ethylhexyl, and decyl.
Preferably, said R is3Selected from the group consisting of oxygen-containing group substituted hydrocarbyl.
When R is3The hydrocarbon group substituted by the oxygen-containing group is selected to be more favorable for the compatibility of the modified dye in the solvent.
Preferably, said R is3Any one selected from 2-hydroxyethyl, methyl sulfonate and isobornyl.
Preferably, said R is1Is methyl.
Preferably, said R is2Is methyl.
Preferably, the dye having a sulfonic acid group includes any one of an anthraquinone-based dye, a phthalocyanine-based dye, a xanthene-based dye, and an azo-based dye.
Preferably, the dye having a sulfonic acid group includes any one of acid blue 113, acid yellow 99, acid red 289, acid green 25, acid red 52, acid red 80, acid green 27, acid blue 25, acid blue 78, acid violet 34, acid violet 43, direct blue 86, direct blue 87, and acid blue 249.
Preferably, the dye having a carboxyl group includes any one of direct green 28, direct yellow 24, direct blue 93, direct blue 149, direct blue 159 and direct blue 163.
The invention also aims to provide a photosensitive resin composition, which comprises the following components in percentage by mass:
the modified dye is 3.1-15% by mass, such as 3.2%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 14.5% and the like.
The mass percentage of the monomer is 2-10%, such as 2.5%, 3.2%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 9%, etc
The mass percentage of the alkali-soluble resin is 1-5%, such as 1.5%, 2%, 2.5%, 3.2%, 3.5%, 4%, 4.5% and the like.
The mass percentage of the initiator is 0.1-1%, such as 0.15%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% and the like.
The photosensitive resin composition provided by the invention comprises the modified dye, the modified dye has good heat resistance, can be well compatible with the alkali-soluble resin, shows high dispersibility, and has excellent heat resistance and developability.
Preferably, the alkali soluble resin includes any one or a combination of at least two of polymethacrylate, polyacrylate, cycloolefin-maleic anhydride copolymer and vinyl ether-maleic anhydride copolymer.
When the alkali soluble resin is selected from the above polymers, it is more compatible with the modified dye, and the photosensitive resin composition has good stability,
preferably, the alkali soluble resin comprises any one or at least two combinations of a copolymer of benzyl acrylate methacrylate, a copolymer of methacrylic acid and benzyl methacrylate, a copolymer of acrylic acid and benzyl methacrylate and maleic anhydride, a copolymer of acrylic acid and benzyl methacrylate and maleimide, a copolymer of methacrylic acid and benzyl methacrylate and maleimide, a copolymer of acrylic acid and benzyl methacrylate and styrene, a copolymer of methacrylic acid and benzyl methacrylate and styrene, a copolymer of acrylic acid and benzyl methacrylate and styrene and 2-hydroxyethyl methacrylate, and a copolymer of methacrylic acid and benzyl methacrylate and styrene and 2-hydroxyethyl methacrylate.
Preferably, the monomer includes methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, decyl acrylate, methyl acrylate sulfonate, isobornyl acrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, diethylene glycol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol diacrylate, butylene glycol diacrylate, propylene glycol diacrylate, butylene glycol, Propylene glycol diacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, decyl methacrylate, methyl methacrylate sulfonate, isobornyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol trimethacrylate, pentaerythritol trimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene, Any one or at least two of dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, trimethylolpropane trimethacrylate, ethylene glycol monomethyl ether methacrylate and propylene glycol dimethacrylate.
Preferably, the initiator comprises 2, 2-azobisisobutyronitrile, 2-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 1-azobis (cyclohexane-1-carbonitrile), diisobutyronitrile, benzoyl methyl ether, benzoyl ethyl ether, benzoyl isobutyl ether, benzil, methyl phenylglyoxylate, any one or at least two of benzoyl tosylate, diethoxyacetophenol, 2-hydroxy-2-methyl-1-phenylpropyl-1-one, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinebenzylphenyl) butanone, p-tert-butyltrichloroacetophenone, benzophenone, isopropylthioxanthone, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide and benzyl dimethyl ketal.
Preferably, the solvent includes any one or a combination of at least two of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol diethyl ether ethyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether, triethylene glycol dimethyl ether, triethylene glycol t-butyl ether, chloroform, and xylene.
The third object of the present invention is to provide a use of the photosensitive resin composition of the second object for a liquid crystal panel.
Preferably, the photosensitive resin composition is used for an optical filter of a liquid crystal panel.
Preferably, the photosensitive resin composition is used as a base resin of a liquid crystal panel filter.
Compared with the prior art, the invention has the following beneficial effects:
(1) the modified dye provided by the invention is a macromolecular dye, and the macromolecular dye is formed by connecting a quaternized polymer and a micromolecular dye with sulfonic acid groups or carboxyl groups, so that the macromolecular dye has good heat resistance same as that of the polymer, is used for a photosensitive resin composition, and can show good dispersibility.
(2) The photosensitive resin composition provided by the invention comprises the modified dye, the modified dye has good heat resistance, can be well compatible with the alkali-soluble resin, shows high dispersibility, and has excellent heat resistance and developability.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
Preparation of modified dye 1:
(1) 180g of butyl acetate and 1.8g of azobisisobutyronitrile are added into a reaction flask and stirred at normal temperature for dissolution. Subsequently, 28.3g of dimethylaminoethyl methacrylate, 34.9g of maleimide, 39g of 2-hydroxyethyl methacrylate and 15.5g of methacrylic acid were added, the mixture was stirred and heated to 110 ℃ and reacted for 3 hours, then 2.4g of dodecanethiol was added and reacted for 20 minutes, the temperature was reduced to room temperature, 2.5g of formic acid was added for acidification, the mixture was stirred for 15 minutes, the polymer was precipitated with 90g of methanol and vacuum-dried at 90 ℃ for 2 hours to obtain a powder of dispersant 1, and the weight-average molecular weight of dispersant 1 as determined by gel permeation chromatography was 5500 and the acid value was 65 mgKOH/g.
The dispersing agent 1 comprises polymerized monomers of dimethylaminoethyl methacrylate, maleimide, 2-hydroxyethyl methacrylate and methacrylic acid in a molar ratio of 3:6:5: 3.
(2) Dissolving 4.5g of the prepared dispersing agent 1 in 30mL of propylene glycol monomethyl ether acetate (PMA), simultaneously dissolving 3.5g of acid green 25 dye and 1.5g of acid yellow 99 dye in 20mL of deionized water, then mixing the dye solution and the dispersing agent solution, stirring for 30 minutes, then dropwise adding 15mL of absolute ethyl alcohol into the mixed solution of the dye and the dispersing agent for precipitation and centrifugation, and taking the precipitate to be dried in vacuum at 90 ℃ for 2 hours to obtain the modified dye 1, wherein the weight-average molecular weight of the modified dye 1 is 7500.
Preparation example 2
The difference from preparation example 1 is that dispersing agent 2 was obtained by replacing dimethylaminoethyl methacrylate with equal amount of dimethylaminoethyl acrylate, the weight average molecular weight of dispersing agent 2 was 5400, the acid value was 65mgKOH/g, modified dye 2 was obtained, and the weight average molecular weight of modified dye 2 was 7500.
Preparation example 3
The difference from preparation example 1 is that 2-hydroxyethyl methacrylate was replaced with an equal amount of 2-hydroxyethyl acrylate to obtain dispersant 3, the weight average molecular weight of dispersant 3 was 5400, the acid value was 65mgKOH/g, and modified dye 3 was obtained, the weight average molecular weight of modified dye 3 was 7500.
Preparation example 4
The difference from preparation example 1 is that step (1) is as follows:
(1) 180g of butyl acetate and 1.6g of azobisisobutyronitrile are added into a reaction flask and stirred at normal temperature for dissolution. Then 48.1g of dimethylaminoethyl methacrylate, 19.8g of maleimide, 26.5g of 2-hydroxyethyl methacrylate and 26.3g of methacrylic acid are added, the temperature is raised to 110 ℃ by stirring and the mixture reacts for 3 hours, 2.5g of dodecanethiol is added to continue the reaction for 30 minutes, the temperature is lowered to room temperature, formic acid is added to acidify the mixture, the mixture is stirred for 15 minutes, 80g of methanol is used for precipitating a polymer, the polymer is dried in vacuum at 90 ℃ for 2 hours, dispersing agent 4 powder is obtained, and the weight average molecular weight of the dispersing agent 4 is 7000 and the acid value is 68mgKOH/g by gel permeation chromatography.
The dispersant 4 comprises polymerized monomers of dimethylaminoethyl methacrylate, maleimide, 2-hydroxyethyl methacrylate and methacrylic acid in a molar ratio of 3:2:2: 3.
Modified dye 4 is obtained, the weight average molecular weight of modified dye 4 is 8700.
Preparation example 5
The difference from preparation example 1 is that step (1) is as follows:
(1) 180g of butyl acetate and 2.0g of azobisisobutyronitrile are added into a reaction flask and stirred at normal temperature for dissolution. Then 16g of dimethylaminoethyl methacrylate, 59.4g of maleimide, 26.5g of 2-hydroxyethyl methacrylate and 8.78g of methacrylic acid are added, the temperature is raised to 110 ℃ by stirring and the reaction is carried out for 3 hours, then 2.2g of dodecanethiol is added, the reaction is continued for 20 minutes, the temperature is reduced to room temperature, formic acid is added for acidification, the stirring is carried out for 15 minutes, 90g of methanol is used for precipitating the polymer, the vacuum drying is carried out for 2 hours at 90 ℃ to obtain dispersing agent 5 powder, the weight average molecular weight of the dispersing agent 5 is 3900 by the gel permeation chromatography, and the acid value is 60 mgKOH/g.
The dispersing agent 5 comprises polymerized monomers of dimethylaminoethyl methacrylate, maleimide, 2-hydroxyethyl methacrylate and methacrylic acid in a molar ratio of 1:6:2: 1.
The modified dye 5 is obtained, and the weight average molecular weight of the modified dye 5 is 5000.
Preparation example 6
The difference from preparation example 1 is that step (1) is as follows:
(1) 180g of butyl acetate and 1.8g of azobisisobutyronitrile are added into a reaction flask and stirred at normal temperature for dissolution. Then 16g of dimethylaminoethyl methacrylate, 19.8g of maleimide, 66.3g of 2-hydroxyethyl methacrylate and 17.6g of methacrylic acid are added, the temperature is raised to 110 ℃ by stirring and the mixture reacts for 3 hours, 2.4g of dodecanethiol is added to continue the reaction for 20 minutes, the temperature is reduced to room temperature, formic acid is added to acidify the mixture, the mixture is stirred for 15 minutes, 90g of methanol is used for precipitating a polymer, the polymer is dried in vacuum at 90 ℃ for 2 hours to obtain dispersing agent 6 powder, and the weight-average molecular weight of the dispersing agent 6 is 5400 and the acid value is 65mgKOH/g as determined by gel permeation chromatography.
The dispersing agent 6 comprises polymerized monomers of dimethylaminoethyl methacrylate, maleimide, 2-hydroxyethyl methacrylate and methacrylic acid in a molar ratio of 1:2:5: 2.
The modified dye 6 was obtained, the weight average molecular weight of the modified dye 6 being 7400.
Preparation example 7
The difference from preparation example 1 is that step (1) is as follows:
(1) 180g of butyl acetate and 1.8g of azobisisobutyronitrile are added into a reaction flask and stirred at normal temperature to be dissolved. Then 8g of dimethylaminoethyl methacrylate, 79.2g of maleimide, 13.3g of 2-hydroxyethyl methacrylate and 4.4g of methacrylic acid are added, the temperature is raised to 110 ℃ by stirring and the reaction is carried out for 3 hours, 2.4g of dodecanethiol is added to continue the reaction for 20 minutes, the temperature is reduced to room temperature, formic acid is added to carry out acidification, the stirring is carried out for 15 minutes, 90g of methanol is used for precipitating the polymer, the vacuum drying is carried out for 2 hours at 90 ℃, and then dispersing agent 7 powder is obtained, and the weight-average molecular weight of the dispersing agent 7 is 4500 and the acid value is 55mgKOH/g by the determination of gel permeation chromatography.
The dispersant 7 comprises polymerized monomers of dimethylaminoethyl methacrylate, maleimide, 2-hydroxyethyl methacrylate and methacrylic acid in a molar ratio of 1:16:2: 1.
The modified dye 7 was obtained, and the weight average molecular weight of the modified dye 7 was 6300.
Preparation example 8
The difference from preparation example 1 is that step (1) is as follows:
(1) 180g of butyl acetate and 1.8g of azobisisobutyronitrile are added into a reaction flask and stirred at normal temperature for dissolution. Then 16g of dimethylaminoethyl methacrylate, 9.9g of maleimide, 93.1g of 2-hydroxyethyl methacrylate and 8.8g of methacrylic acid are added, the temperature is raised to 110 ℃ by stirring and the reaction is carried out for 3h, 2.4g of dodecanethiol is added to continue the reaction for 20min, the temperature is reduced to room temperature, formic acid is added to carry out acidification, the stirring is carried out for 15min, 90g of methanol is used for precipitating the polymer, the vacuum drying is carried out for 2h at 90 ℃ to obtain dispersing agent 8 powder, and the weight average molecular weight of the dispersing agent 8 is 6000 and the acid value is 62mgKOH/g by the determination of gel permeation chromatography.
The dispersant 8 comprises polymerized monomers of dimethylaminoethyl methacrylate, maleimide, 2-hydroxyethyl methacrylate and methacrylic acid in a molar ratio of 1:1:7: 1.
A modified dye 8 was obtained, the modified dye 8 having a weight average molecular weight of 8500.
Preparation example 9
The difference from preparation example 1 is that step (1) is as follows:
(1) 180g of butyl acetate and 1.8g of azobisisobutyronitrile are added into a reaction flask and stirred at normal temperature for dissolution. Then 96g of dimethylaminoethyl methacrylate, 19.8g of maleimide, 13.3g of 2-hydroxyethyl methacrylate and 8.8g of methacrylic acid are added, the mixture is stirred and heated to 110 ℃ and reacted for 3 hours, then 2.4g of dodecanethiol is added and reacted for 20 minutes, the temperature is reduced to room temperature, formic acid is added for acidification, the mixture is stirred for 15 minutes, 90g of methanol is used for precipitating the polymer, vacuum drying is carried out at 90 ℃ for 2 hours, so that dispersing agent 9 powder is obtained, and the weight average molecular weight of the dispersing agent 9 is 7000 and the acid value is 65mgKOH/g as measured by gel permeation chromatography.
The dispersing agent 9 comprises polymerized monomers of dimethylaminoethyl methacrylate, maleimide, 2-hydroxyethyl methacrylate and methacrylic acid in a molar ratio of 6:2:1: 1.
The modified dye 9 is obtained, and the weight average molecular weight of the modified dye 9 is 10000.
Preparation example 10
The difference from preparation example 1 is that step (1) is as follows:
(1) 180g of butyl acetate and 1.85g of azobisisobutyronitrile are added into a reaction flask and stirred at normal temperature for dissolution. Subsequently, 32g of dimethylaminoethyl methacrylate, 9.9g of maleimide, 13.3g of 2-hydroxyethyl methacrylate and 52.8g of methacrylic acid were added, the mixture was stirred and heated to 110 ℃ and reacted for 3 hours, then 2.4g of dodecanethiol was added, the reaction was continued for 20 minutes, the temperature was reduced to room temperature, formic acid was added for acidification, stirring was carried out for 15 minutes, the polymer was precipitated with 90g of methanol and vacuum-dried at 90 ℃ for 2 hours to give a dispersant 10 powder, and the weight average molecular weight of the dispersant 10 as determined by gel permeation chromatography was 4200 and the acid value was 75 mgKOH/g.
The dispersant 10 comprises polymerized monomers of dimethylaminoethyl methacrylate, maleimide, 2-hydroxyethyl methacrylate and methacrylic acid in a molar ratio of 2:1:1: 6.
Modified dye 10 is obtained, said modified dye 10 having a weight average molecular weight of 6100.
Preparation example 11
Preparation of modified dye 11:
(1) 182g of dimethylbenzene and 1.82g of dibenzoyl peroxide are added into a reaction flask and stirred at normal temperature to be dissolved. Then 27.9g of dimethylaminoethyl acrylate, 31.6g of maleimide, 72.2g of isobornyl methacrylate and 22.4g of methacrylic acid are added, the temperature is raised to 120 ℃ by stirring and the reaction is carried out for 2.5h, then 2.6g of dodecanethiol is added, the reaction is continued for 20min, the temperature is reduced to room temperature, 34.4g of octyl bromide is added, the mixture is heated and stirred for 1h at 50 ℃, 98g of methanol is used for precipitating the polymer and vacuum drying is carried out for 2h at 90 ℃, so that the dispersing agent 11 powder is obtained, the weight average molecular weight (determined by gel permeation chromatography) of the dispersing agent 11 is 6000, and the acid value is 65 mgKOH/g.
The dispersant 11 comprises polymerized monomers of dimethylaminoethyl acrylate, maleimide, isobornyl methacrylate and methacrylic acid in a molar ratio of 3:5:5: 4.
(2) Dissolving 5g of acid red 289 dye in 20mL of deionized water, dissolving 5g of prepared dispersing agent 11 in 30mL of propylene glycol monomethyl ether acetate (PMA), mixing the dye solution and the dispersing agent solution, stirring for 30 minutes, then dropwise adding 15mL of anhydrous ethanol into the mixed solution of the dye and the dispersing agent for precipitation and centrifugation, and drying the precipitate at 90 ℃ for 2 hours in vacuum to obtain the modified dye 11 with the weight-average molecular weight of 8500.
Example 1
Dispersing the modified dye 1 into a photosensitive resin composition consisting of propylene glycol monomethyl ether acetate (solvent, PMA), acrylate copolymer (alkali-soluble resin, Showa BSR-3), dipentaerythritol hexaacrylate (monomer), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (initiator, TPO, Basff), gamma-glycidyl ether propyl trimethoxy silane coupling agent and DC-7 (leveling agent, Dow Corning), wherein the photosensitive resin composition comprises the following components in percentage by weight:
example 2
The difference from example 1 is that modified dye 1 is replaced with modified dye 2.
Example 3
The difference from example 1 is that modified dye 1 is replaced with modified dye 3.
Example 4
The difference from example 1 is that modified dye 1 is replaced with modified dye 4.
Example 5
The difference from example 1 is that modified dye 1 is replaced with modified dye 5.
Example 6
The difference from example 1 is that modified dye 1 is replaced with modified dye 6.
Example 7
The difference from example 1 is that modified dye 1 is replaced with modified dye 7.
Example 8
The difference from example 1 is that modified dye 1 is replaced with modified dye 8.
Example 9
The difference from example 1 is that modified dye 1 is replaced with modified dye 9.
Example 10
The difference from example 1 is that modified dye 1 is replaced with modified dye 10.
Example 11
Dispersing a modified dye 11 into a photosensitive resin composition consisting of propylene glycol monomethyl ether acetate (solvent), acrylate copolymer (alkali-soluble resin, showa BSR-3), dipentaerythritol hexaacrylate (monomer), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (initiator, basf), gamma-glycidyl ether propyl trimethoxy silane coupling agent and DC-7 (leveling agent, Dow Corning), wherein the photosensitive resin composition comprises the following components in percentage by weight:
example 12
Dispersing the modified dye 1 into a photosensitive resin composition consisting of propylene glycol monomethyl ether acetate (solvent), acrylate copolymer (alkali-soluble resin, SHOWA and BSR-3), methyl acrylate (monomer), 2-azobisisobutyronitrile (initiator), gamma-glycidyl ether propyl trimethoxy silane coupling agent and DC-7 (leveling agent, Dow Corning), wherein the photosensitive resin composition comprises the following components in percentage by weight:
example 13
Dispersing the modified dye 1 into a photosensitive resin composition consisting of ethylene glycol monomethyl ether (solvent), acrylate copolymer (alkali-soluble resin, Showa BSR-3), dipentaerythritol hexaacrylate (monomer), benzoyl methyl ether (initiator), gamma-glycidyl ether propyl trimethoxy silane coupling agent and DC-7 (leveling agent, Dow Corning), wherein the photosensitive resin composition comprises the following components in percentage by weight:
comparative example 1
The difference from example 1 is that modified dye 1 is replaced by modified dye D1, and modified dye D1 is prepared as follows:
4.5g of BYK-164 (Germany Bike) dispersant is dissolved in 30mL of propylene glycol monomethyl ether acetate (PMA), 3.5g of acid green 25 dye and 1.5g of acid yellow 99 dye are dissolved in 20mL of deionized water, then the dye solution and the dispersant solution are mixed and stirred for 30 minutes, then 15mL of absolute ethyl alcohol is added into the mixed solution of the dye and the dispersant dropwise for precipitation and centrifugation, and the precipitate is dried in vacuum at 90 ℃ for 2 hours to obtain a modified dye D1, wherein the weight-average molecular weight of the modified dye D1 is 7800.
Comparative example 2
The difference from example 1 is that modified dye 1 is replaced by modified dye D2, and modified dye D2 is prepared as follows:
5g of BYK-163 dispersant (Germany Bike) was dissolved in 30mL of propylene glycol monomethyl ether acetate (PMA), while 3.5g of acid Green 25 dye and 1.5g of acid yellow 99 dye were dissolved in 20mL of deionized water, the dye solution and the dispersant solution were mixed and stirred for 30 minutes, then 15mL of absolute ethanol was added dropwise to the mixture of dye and dispersant to precipitate and centrifuged, and the precipitate was dried under vacuum at 90 ℃ for 2 hours. The modified dye D2 was obtained, the weight average molecular weight of the modified dye D2 being 7400.
Comparative example 3
The difference from example 1 is that modified dye 1 was replaced with modified dye D3, and the preparation method of modified dye D3 was different from that of preparation example 1 in that dimethylaminoethyl methacrylate was not added.
Comparative example 4
The difference from example 1 is that modified dye 1 is replaced by modified dye D4, and modified dye D4 is prepared as follows:
(1) 180g of butyl acetate and 2.5g of azobisisobutyronitrile are added into a reaction flask and stirred at normal temperature for dissolution. 28.3g of dimethylaminoethyl methacrylate, 34.9g of maleimide, 39g of 2-hydroxyethyl methacrylate and 15.5g of methacrylic acid are added, the mixture is stirred and heated to 110 ℃ and reacted for 3 hours, then 2.4g of dodecanethiol is added, the reaction is continued for 20 minutes, the temperature is reduced to room temperature, 2.5g of formic acid is added for acidification, the mixture is stirred for 15 minutes, 90g of methanol is used for precipitating a polymer, the polymer is dried in vacuum at 90 ℃ for 2 hours to obtain powder D4, and the dispersant D4 is obtained and has the weight-average molecular weight of 2500 and the acid value of 65mgKOH/g as determined by gel permeation chromatography.
The dispersing agent D4 comprises four polymerized monomers of dimethylaminoethyl methacrylate, maleimide, 2-hydroxyethyl methacrylate and methacrylic acid in a molar ratio of 3:6:5:3
(2) Dissolving 4.5g of the prepared dispersant 1 in 30mL of propylene glycol monomethyl ether acetate (PMA), simultaneously dissolving 3.5g of acid green 25 dye and 1.5g of acid yellow 99 dye in 20mL of deionized water, then mixing the dye solution and the dispersant solution, stirring for 30 minutes, then dropwise adding 15mL of absolute ethyl alcohol into the mixed solution of the dye and the dispersant, precipitating and centrifuging, and taking the precipitate to be dried in vacuum at 90 ℃ for 2 hours to obtain a modified dye D4, wherein the weight-average molecular weight of the modified dye D4 is 4000.
Performance testing
The photosensitive resin compositions prepared in examples and comparative examples were subjected to photolithography under the same conditions, and the development time, the transmittance Y value, and the color change rate Δ Eab under 20min post-baking conditions at 230 ℃ were measured, respectively, the development time being the time taken to develop a pattern and being an index for evaluating the developability, the smaller the development time, the better the developability of the composition, and the Y and Δ Eab values were measured using a konica minolta CM-5 spectrophotometer. The test results are shown in table 1.
TABLE 1
As can be seen from table 1, the comparative examples and comparative examples show that the photosensitive resin compositions in the examples have short development time, low color change rate, high transmittance, and excellent developability and heat resistance, and in addition, the photosensitive resin compositions in the examples have no agglomeration phenomenon during the standing and application processes and exhibit excellent dispersion stability; in comparison examples 1 and 2, the macromolecular modified dye in example 1 is replaced by a modified dye formed by combining a common dispersant and a dye, so that the development time and the color change rate are obviously increased, and the transmittance is reduced, which proves that when the macromolecular modified dye formed by connecting the quaternized polymer and the micromolecular dye with sulfonic acid group or carboxyl group provided by the invention is used for a photosensitive resin composition, the macromolecular modified dye has more excellent heat resistance and development performance; in comparative example 3, a modified dye was prepared by using a polymer not containing a dimethylaminoethyl methacrylate structural unit in combination with a dye, so that the development time and the color change rate of a photosensitive resin composition containing the modified dye were significantly increased, and the transmittance was decreased, demonstrating that the presence of a quaternary ammonium group is one of the important conditions under which the modified dye can improve the developability and heat resistance of the photosensitive resin composition; comparative example 4 selects a modified dye having a molecular weight of less than 5000, and the obtained photosensitive resin composition has an remarkably increased development time and color change rate and a decreased transmittance, demonstrating that when the molecular weight of the modified dye is too small, the degree of improvement of the modified dye on the development performance and heat resistance of the photosensitive resin composition is greatly reduced. The modified dye is a macromolecular dye with the molecular weight of 5000-10000, and the macromolecular dye is formed by connecting a quaternized polymer and a micromolecular dye with a sulfonic group or a carboxyl group. Therefore, the photosensitive resin composition has good heat resistance same as that of a polymer, can be well compatible with the alkali-soluble resin, shows high dispersibility, and simultaneously has excellent heat resistance and developability.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (18)
1. A modified dye, characterized in that the modified dye comprises at least one structural unit (a), at least one structural unit (B), at least one structural unit (C) and at least one structural unit (D);
said X—Selected from dye anions having sulfonic acid groups—SO3Dye or carboxyl-bearing Dye anions—OOC-Dye；
The R is1、R2And R4Each independently selected from methyl or hydrogen;
the R is3Any one selected from hydrocarbyl or oxygenated group-substituted hydrocarbyl;
the R is5Any one selected from hydrogen, benzyl and C1-C12 alkyl;
the number of the structural units (A) is n1The total number of structural units in the modified dye is n;
n is1The/n is any value of 0.05-0.6;
the number of the structural units (B) is n2N is said n2The/n is any value of 0.1-0.7;
the number of the structural units (C) is n3N is said n3The/n is any value of 0.1-0.6;
the weight average molecular weight of the modified dye is 5000-10000.
2. The modified dye of claim 1, wherein n is1The value of/n is 0.1 to 0.3.
3. The modified dye of claim 1, wherein n is n2The value of/n is 0.2 to 0.6.
4. According to the rightThe modified dye of claim 1, wherein n is3The value of/n is 0.2 to 0.5.
5. The modified dye according to claim 1, wherein the number of the structural unit (D) is n4N is said to4The value of/n is 0.05 to 0.6.
6. The modified dye of claim 5, wherein n is4The/n is an arbitrary value of 0.1 to 0.3.
7. The modified dye according to claim 1 or 2, wherein n is2The value of/n is 0.1-0.7, wherein n3The value of/n is 0.1 to 0.6, and the number of the structural units (D) is n4N is said n4The value of/n is 0.05 to 0.6.
8. The modified dye of claim 1, wherein R is3Selected from C1-C12 hydrocarbon groups.
9. The modified dye of claim 8, wherein R is3Selected from any one of methyl, ethyl, n-butyl, isobutyl, tert-butyl, n-dodecyl, 2-ethylhexyl and decyl.
10. The modified dye of claim 1, wherein R is3Selected from the group consisting of oxygen-containing group substituted hydrocarbyl.
11. The modified dye of claim 1, wherein R is3Any one selected from 2-hydroxyethyl, methyl sulfonate and isobornyl.
12. The modified dye of claim 1, wherein R is1Is methyl.
13. The modified dye of claim 1, wherein R is2Is methyl.
14. The modified dye according to claim 1, wherein the dye having a sulfonic acid group comprises any one of an anthraquinone-based dye, a phthalocyanine-based dye, a xanthene-based dye, and an azo-based dye.
15. The photosensitive resin composition is characterized by comprising the following components in percentage by mass:
16. use of the photosensitive resin composition according to claim 15 for a liquid crystal panel.
17. Use according to claim 16, wherein the photosensitive resin composition is used for an optical filter of a liquid crystal panel.
18. Use according to claim 17, wherein the photosensitive resin composition is used as a matrix resin for a liquid crystal panel filter.
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