CN110389498B - Photocurable resin composition, optical filter and photoresist - Google Patents
Photocurable resin composition, optical filter and photoresist Download PDFInfo
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- CN110389498B CN110389498B CN201810367500.7A CN201810367500A CN110389498B CN 110389498 B CN110389498 B CN 110389498B CN 201810367500 A CN201810367500 A CN 201810367500A CN 110389498 B CN110389498 B CN 110389498B
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—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
Abstract
The invention provides a light-cured resin composition, an optical filter and a photoresist. A photocurable resin composition comprising a photosensitive resin, an initiator, and a photopolymerizable monomer, the photosensitive resin having the following structural formula I:
Description
Technical Field
The invention relates to the field of optical materials, in particular to a light-cured resin composition, an optical filter and a photoresist.
Background
The photo-curing resin composition is an important raw material for preparing the optical filter, and the quality of the performance of the photo-curing resin composition directly determines the quality of the optical filter, thereby influencing the quality of the performance of a Liquid Crystal Display (LCD). In order to ensure the heat resistance, chemical resistance and other properties in the process of manufacturing the optical filter, higher requirements are put on the properties of the photosensitive resin composition. Polymer compounds having a fluorene skeleton have excellent characteristics such as high heat resistance, high transparency, high refractive index, and low expansion coefficient, and patent documents CN100564349C and CN101965375A disclose: the fluorine-containing polymer compound can solve the problem that the traditional light-cured resin composition cannot achieve high refractive index and high heat resistance to a certain extent. However, with the development of the photoelectron industry, the requirements for straightness, alkali solubility and the like of patterns formed on the photo-curing material are higher and higher, and the performance of the resin composition containing the fluorene skeleton reported in the existing patent is difficult to satisfy the requirements in all aspects. Particularly, the photocuring rate is not satisfactory, and the requirements on the moldability of a fine pattern, the adhesion to a substrate, the alkali solubility, the solvent resistance and the like are difficult to meet.
Disclosure of Invention
The invention mainly aims to provide a photocuring resin composition, an optical filter and a photoresist, and aims to solve the problems that the photocuring resin composition in the prior art is not ideal in photocuring rate and difficult to meet the requirements on alkali solubility and solvent resistance.
In order to achieve the above object, according to one aspect of the present invention, there is provided a photocurable resin composition comprising a photosensitive resin, an initiator, and a photopolymerizable monomer, the photosensitive resin having the following structural formula I:
in the structural formula I, R1Is hydrogen, C1～C10Straight chain alkyl group of (1), C3～C10Branched alkyl of C6～C20Aryl and C1～C10Any one of the alkoxy groups of (a); m is1、m2Each independently is any integer of 0 and 1-4, n1、n2Each independently is any integer of 0 and 1-3; r2Is H, C1～C10Straight chain alkyl of (2) and C3～C10Any one of the branched alkyl groups of (a); r3、R4、R5And R6Each independently is H, C1～C 20A straight-chain alkyl group of3～C10Branched alkyl of C3～C20Cycloalkyl of, C6～C20Aryl of (A), C2～C10And R is any one of a group having one or more unsaturated C ═ C bonds, a group having one or more epoxy functional groups, a group having one or more hydroxyl functional groups, and a group having one or more amino groups3、R4、R5And R6One or more of C may be substituted with O, S, N, P, and R3、R4、R5And R6At least one of which is H, A, B each independently represents a substituent group, and n is any one of 1 to 20An integer number.
Further, a is selected from any one of the following groups:
denotes the attachment position of the anhydride.
Further, the above B is selected from any one of the following groups:
denotes the attachment position of the anhydride.
Further, the above R1Is hydrogen or methyl.
Further, m is as defined above1、m2、n1And n2Each independently 0 or 1.
Further, the above R2Is C1～C5Straight chain alkyl or C3～C5Any of the branched alkyl groups of (a).
Further, the above R3、R4、R5And R6At least one is H, but not all are H at the same time.
Further, the acid value of the photosensitive resin is 1 to 130mgKOH/g, preferably 70 to 120 mgKOH/g.
Further, the photosensitive resin is 20 to 50 parts by mass, preferably 25 to 35 parts by mass; the mass part of the initiator is 0.1-10 parts, preferably 0.5-5 parts; the mass part of the photopolymerizable monomer is 1 to 25 parts, preferably 10 to 20 parts.
Further, the initiator is one or a combination of more of benzophenone initiator, triazine initiator, dialkoxy acetophenone initiator, alpha-hydroxyalkyl benzophenone initiator, alpha-amine alkyl benzophenone initiator, acyl phosphine oxide initiator, benzophenone initiator, benzoin initiator, benzil initiator, heterocyclic aromatic ketone initiator and oxime ester photoinitiator.
The photocurable resin composition further comprises a colorant, and the mass part of the colorant is preferably 1-10 parts, and more preferably 1-5 parts.
Further, the photo-curable resin composition further comprises a solvent, and the solvent is preferably added in an amount such that the solid content of the photo-curable resin composition is 1 to 55wt%, and more preferably 30 to 55 wt%.
According to another aspect of the present invention, there is provided an optical filter prepared from the photocurable resin composition, which is any one of the photocurable resin compositions described above.
According to another aspect of the present invention, there is provided a photoresist comprising the photocurable resin composition of any one of the above.
By applying the technical scheme of the invention, compared with the carboxylic acid group content of the conventional similar photosensitive resin in the prior art, the carboxylic acid group content of the photosensitive resin with the structural formula I is lower, and the content of active groups such as side chain alcoholic hydroxyl or epoxy groups is increased, so that the acid value of the photosensitive resin is further reduced, the reaction activity and the curing rate are improved, and the photocuring performance, the adhesion to a substrate, the alkali-resistant solvent resistance and the solvent resistance of the obtained modified photosensitive resin are further improved.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background art of the present application, the photocurable resin composition of the prior art has an unsatisfactory photocuring rate, and is difficult to meet the requirements on the formability of micro patterns, the adhesion to a substrate, the alkali-resistant solubility, the solvent resistance, and the like.
In one exemplary embodiment of the present application, there is provided a photocurable resin composition including a photosensitive resin having the following structural formula I:
in the structural formula I, R1Is hydrogen, C1～C10Straight chain alkyl group of (1), C3～C10Branched alkyl of C6～C20Aryl and C1～C10Any one of the alkoxy groups of (a); m is1、m2Each independently is any integer of 0 and 1-4, n1、n2Each independently is any integer of 0 and 1-3; r2Is H, C1～C10Straight chain alkyl of (2) and C3～C10Any one of the branched alkyl groups of (a); r3、R4、R5And R6Each independently is H, C1～C 20Direct alkyl of (1), C3～C10Branched alkyl of C3～C20Cycloalkyl of, C6～C20Aryl of (A), C1～C 10And R is any one of a group having one or more unsaturated C ═ C bonds, a group having one or more epoxy functional groups, a group having one or more hydroxyl functional groups, and a group having one or more amino groups3、R4、R5And R6One or more of C may be substituted with O, S, N, P, and R3、R4、R5And R6At least one of the groups is H, A, B independently represents a substituent group, and n is any integer of 1-20.
Compared with the conventional similar photosensitive resin in the prior art, the content of the carboxylic acid groups of the photosensitive resin with the structural formula I is less, and the content of active groups such as side chain alcoholic hydroxyl groups or epoxy groups is increased, so that the acid value of the photosensitive resin is further reduced, the reaction activity and the curing rate are improved, and the photocuring performance, the adhesion to a substrate, the alkali-resistant solvent resistance and the solvent resistance of the obtained modified photosensitive resin are further improved.
The substituent group represented by a in the structural formula I may be theoretically any chemically acceptable group, and in order to further optimize the advantages of the photosensitive resin, it is preferable that a be selected from any one of the following groups:
denotes the attachment position of the anhydride.
The substituent group represented by B in the structural formula I may be theoretically any chemically acceptable group, and in order to stabilize the performance of the photosensitive resin, it is preferable that B is selected from any one of the following groups:
denotes the attachment position of the anhydride.
R is preferred for ease of synthesis and for ensuring long-term stability of the photosensitive resin1Is hydrogen or methyl. m is1、m2、n1And n2Each independently 0 or 1. R2Is C1～C5Straight chain alkyl or C3～C5Any of the branched alkyl groups of (a). R3、R4、R5And R6At least one is H, but not all are H at the same time. Preferably, n is an integer of 1 to 10
Further, the acid value of the photosensitive resin is preferably 1 to 130mgKOH/g, more preferably 70 to 120 mgKOH/g.
The photosensitive resin can be prepared by reacting commercially available alkali-soluble resin (having a structural formula II) with epoxy compounds, alcohol compounds and amine compounds in the presence of a solvent. Such as alkali soluble resin, propylene oxide compounds, primary alcohols and primary amines.
R in the above formula II1，R2，A，B，m1，m2，n，n1，n2Are all the same as the meanings shown in the structural formula I.
The epoxy compound, the alcohol compound and the amine compound may be selected from the following compounds:
in a preferred embodiment of the present application, in the photocurable resin composition, the mass part of the photosensitive resin is 20 to 50 parts, preferably 25 to 35 parts; the mass part of the initiator is 0.1-10 parts, preferably 0.5-5 parts; the mass part of the photopolymerizable monomer is 1 to 25 parts, preferably 10 to 20 parts. By blending the above components in parts by weight, the rapid curing performance of the photosensitive resin is sufficiently exhibited, and the curing effect is further improved.
The initiator in the photocurable resin composition may be mixed in a state of being dissolved or dispersed in a solvent, or may be chemically bonded to the photosensitive resin. The initiator used in the present invention is not particularly limited, and may be selected from one or a combination of more of benzophenone-based initiators, triazine-based initiators, dialkoxybenzophenone-based initiators, α -hydroxyalkylphenone-based initiators, α -aminoalkylphenone-based initiators, acylphosphine oxide initiators, benzophenone-based initiators, benzoin-based initiators, benzil-based initiators, heterocyclic arone-based initiators, and oxime ester-based photoinitiators. Oxime ester initiators are particularly preferred.
An exemplary list is: benzophenone, 4-phenylbenzophenone, 4-benzoyl-4' -methyldiphenylsulfide, diethoxyacetophenone, 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, benzoin methyl ether, benzoin isobutyl ether, 2-ethyl-9, 10-dimethoxyanthracene, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9, 10-phenanthrenequinone, o-ethoxycarbonyl-a-oxyimino-1-phenylpropan-one, 1, 2-octanedione, methyl ethyl acetate, or ethyl acetate, or ethyl acetate, or a-2-acetate, or a salt, 1- (4-phenylthio) phenyl-2 (O-benzoyloxime), 1- (9-ethyl) -6- (2-methylbenzoyl) carbazol-3 yl-1- (O-acetyloxime), GGI-124, GGI-224, OXE-01, NCI-831, 2,4, 5-triarylimidazole dimer, 4 '-bisdiethylaminobenzophenone, 4' -dichlorobenzophenone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, trichloroacetophenone, amyl-4-dimethylaminobenzoate, 9-phenylacridine, 1, 7-bis (9-acridinyl) heptane, 1, 3-bis (9-acridinyl) propane, 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) vinyl ] -4, 5-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2, 4-bis (trichloromethyl) -6- (2-bromo-4-methoxy) phenyl-s-triazine, 2, 4-bis (trichloromethyl) -6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2, 4-bis (trichloromethyl) -6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 2-bis (trichloromethyl) -6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 4-benzoyl-4' -methyl dimethyl sulfide, 4-dimethyl ethyl aminobenzoate, 4-dimethyl methyl aminobenzoate, benzyl-beta-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1, 2-propanedione-2 (o-ethoxycarbonyl) oxime, and the like.
The photopolymerizable monomer used in the photocurable resin composition is used to improve the properties of the photocurable resin composition, such as photosensitivity, mechanical strength, crosslinking property, and chemical resistance. As the polymerizable monomer, any one or a combination of several kinds thereof may be selected as necessary as long as it is a monomer having one or more unsaturated bonds in the molecule. Illustrative examples of the photopolymerizable monomers selected in the present invention include: (meth) acrylic acid adducts of epoxy compounds such as propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol triglycidyl ether, and glycerol triglycidyl ether; unsaturated organic acids such as maleic acid and anhydrides thereof; acrylamides such as N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-methylolacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N-methylolmethacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-dimethylmethacrylamide, and N, N-diethylmethacrylamide; polyethylene glycol di (meth) acrylate (the number of ethylene groups is 2 to 14); trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane propoxytis tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, polypropylene glycol di (meth) acrylate (propylene number is 2 to 14); dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol a polyoxyethylene di (meth) acrylate, bisphenol a ethylenedioxy di (meth) acrylate, esters of polycarboxylic acids (such as phthalic anhydride) with compounds having hydroxyl groups and ethylenically unsaturated groups (such as β -hydroxyethyl (meth) acrylate), alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.; styrenes such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, styrene, and hydroxystyrene; n-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylimidazole, etc.; the above-listed substances may be used alone or in combination of two or more.
The above-mentioned photocurable resin composition may further optionally contain a colorant commonly used in the art according to the application requirements of the product, and a color filter may be well formed by adding the colorant. Preferably, the photocurable resin composition further comprises a colorant.
Any organic pigment, inorganic pigment, which is generally used in the art may be selectively used as the colorant of the present application. These include water-soluble pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, indoleanthrone pigments, indanthrone pigments, diketopyrrolopyrrole pigments, and the like. The pigments can be used singly or after being mixed, and are determined according to specific requirements of products.
Further preferred are organic raw materials, and specific pigments are exemplified below, but not limited to, the following pigments. Compounds with a color index (The Society of Dyers and Colorists) (C.I.) number are listed as follows:
c.i. pigment orange 1,3, 11, 13, 14, 15, 16, 17, 20, 24, 3, 53, 55, 60, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 100, 101, 106, 109, 120, 125, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 167, 175, 180, 183, 185;
c.i. pigment orange 1, 13, 31, 36, 42, 43, 55, 59, 61, 65, 71;
c.i. pigment violet 1, 14, 19, 23, 29, 30, 36, 37, 38, 39, 40;
c.i. pigment red 1,2, 3, 4,5, 6, 7, 8, 9,10, 11, 12, 14, 15, 16, 18, 19, 21, 23, 30, 31, 37, 38, 40, 42, 48, 53:1, 57:2, 60:1, 83, 97, 105, 122, 144, 166, 176, 180, 192, 202, 206, 207, 208, 215, 224, 242, 254, 255, 264, 265;
c.i. pigment blue 1,2, 15:3, 15:6, 16, 21, 22, 60, 64, 66;
c.i. pigment green 7, 10, 15, 25, 36, 47, 48;
c.i. pigment brown 23, 25, 26, 28;
c.i. pigment black 1 and 7, etc.
When the colorant is used as a light-shading agent, a black pigment is preferably used, and examples of the black pigment include carbon black, titanium black, metal oxides such as copper, iron, and manganese, composite oxides, metal sulfides, metal sulfates, and metal carbonates. Among them, carbon black having a high light-shielding property is preferable. The content of the colorant may be determined appropriately according to the use of the photocurable resin composition, and is preferably 1 to 10 parts by mass, more preferably 3 to 5 parts by mass. In order to uniformly disperse the colorant in the photosensitive resin composition, a dispersant may also be used. As such a dispersant, a polyethyleneimine, a urethane resin-based, or an acrylic resin-based polymer dispersant, particularly an oleic acid acrylic resin-based dispersant, is preferably used.
When the photosensitive resin composition of the present invention is used for applications such as optical filter production, a solvent for dispersion is required. Therefore, the photocurable resin composition preferably further comprises a solvent, and as a commonly used solvent, (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. can be selected; aromatic hydrocarbons, for example: toluene, xylene, trimethylbenzene, etc.; amide compounds, such as: n-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, and the like; carboxylic acid ester compounds, for example: ethyl 2-oxobutyrate, methyl acetoacetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl acetone, methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutylacetate, isopropyl acetate, butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, butyl propionate, ethyl butyrate, butyl propionate, ethyl, 3-methyl-3-methoxybutyl propionate and the like; solvents of the same type, for example: methyl ethyl ketone, cyclohexanone, heptanone, 3-heptanone, and the like; cyclic ether compounds such as tetrahydrofuran, pyran, and the like; cyclic ester compounds such as gamma-butyrolactone, etc.
The organic solvent may be used alone or in combination of two or more, wherein the solvents such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol methyl ethyl ether and the like have good solubility for the photosensitive resin composition of the present invention; further preferred solvents are propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether. The amount of the solvent added is preferably such that the solid content of the photocurable resin composition is 1 to 55wt%, more preferably 30 to 55 wt%.
In another preferred embodiment of the present application, the photocurable resin composition may contain additives such as, but not limited to, a sensitizer, a filler, a curing agent, a leveling agent, an adhesion promoter, an antioxidant, or an ultraviolet absorber. For example, 0.1 to 5 parts by mass of a sensitizer is preferable, and 0.1 to 2 parts by mass is preferable; 0.1 to 5 parts by mass of a leveling agent, preferably 0.1 to 1.0 part by mass.
Among them, the curing agent is used to improve deep curability and mechanical strength. As the curing agent, specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound and the like can be used, but not limited to these compounds. The leveling agent may be a commercially available surfactant, and specifically, may include silicone surfactants, ester surfactants, ionic surfactants, nonionic surfactants, amphoteric surfactants, and the like, and these surfactants may be used alone or in combination of two or more. The adhesion promoter may be a silane compound, and specific examples thereof include: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -30-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. The adhesion promoters may be used alone or in combination of two or more. Specific examples of the antioxidant include: 4,4 '-butylidenebis (6-tert-butyl-3-methylphenol), 2, 6-di-tert-butyl-4-methylphenol, 2,3' -thiobis (4-methyl-6-tert-butylphenol), p-methoxyphenol and the like. The ultraviolet absorbent can be 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc.
In another exemplary embodiment of the present application, there is provided an optical filter prepared from a photocurable resin composition, which is any one of the photocurable resin compositions described above. The photocuring resin composition has improved photocuring performance, adhesion to a substrate, alkali-resistant solvent resistance and solvent resistance, so that the optical performance of the optical filter prepared by using the photocuring resin composition is improved.
In still another exemplary embodiment of the present application, there is provided a photoresist including a photocurable resin composition, the photocurable resin composition being any one of the photocurable resin compositions described above. The photo-curing resin composition has the advantage of higher pattern linearity, and the photo-curing effect is improved.
The present invention will be described more specifically with reference to the following examples. It should be noted that, in the case of no conflict, the embodiments in this application are only for further explaining the features of the above invention, and are not limited to the methods and features mentioned in the embodiments.
1. Synthesis of photosensitive resin
Accurately weighing commercially available alkali-soluble resin II1000g, 2.5g of tetrabutylammonium bromide and 0.25g of p-methoxyphenol, and adding the materials into a 2L reaction bottle; starting stirring, adding 50g of epoxy compound (or alcohol compound or amine compound), introducing dry air, heating to 110 ℃, stirring and reacting for 6h, stopping the reaction when the acid value of the system is 100-. Cooling to 70 ℃, and filtering by a 0.8 μm membrane to obtain a target product, namely the photosensitive resin I.
According to the experimental procedure of example 1, photosensitive resins of different structures can be prepared using different raw materials. A photosensitive resin having a structure such as A1-A12 was obtained exemplarily. Specific examples are shown in the following table:
2. preparation of photosensitive resin composition
Compositions shown in examples 1 to 14 and comparative examples 1 to 2 were prepared exemplarily according to the relevant raw material components listed in Table 1 with reference to the following proportions, and the raw materials were mixed uniformly.
The light-cured resin composition comprises the following components in percentage by weight: % (mass fraction)
TABLE 1
In the table, the structure of the alkali-soluble resin B in the comparative example is:
3. Evaluation of application Properties of photosensitive composition
The photosensitive resin compositions of examples 1 to 14 and comparative examples 1 to 2 were tested by applying them onto a glass substrate (100 mm. times.100 mm) using a spin coater, and prebaked at 90 ℃ for 90 seconds to form a coating film having a thickness of 1.0. mu.m. Then, the exposure gap was set to 50 μm using a mirror projection alignment exposure apparatus, and exposure was performed through a negative mask in which a line pattern of 20 μm was formed. The exposure amount was set to 20, 40, 60, 120mJ/cm24 grades. One of the exposed sample coating films was developed in a 0.04 mass% KOH aqueous solution at 26 ℃ for 40s, and the remaining sample coating films were respectively developed in a 0.04 mass% KOH aqueous solution at 26 ℃ for 60s, 80s, and 230 ℃ for 30 minutes and post-baked to form a line pattern, and the linearity and the development residual film rate thereof were tested. The higher the developing residual film rate, the better the adhesion.
Similarly, the coating film was irradiated with ultraviolet light at an exposure gap of 50 μm through a negative mask having a linear pattern of 2, 5, 10, or 20 μm, and the exposure amount was set to 20mJ/cm2、40mJ/cm2、60mJ/cm2、120mJ/cm2. The exposed coating film was developed in a 0.04 mass% KOH aqueous solution at 26 ℃, and then post-baked at 230 ℃ for 30min to form a line pattern.
The formed linear pattern was observed with an optical microscope to evaluate the linearity and adhesion of the pattern. The evaluation results are shown in the following table, and the pattern straightness was evaluated according to the following criteria:
very good: smooth and non-sawtooth pattern line edge
O: the edge of the pattern line is smooth and has a small amount of saw teeth;
and (delta): the pattern line edge is irregular;
the pattern adhesion was evaluated according to the following criteria:
very good: when the pattern is formed, the number of the residual patterns in the coating film after development is 95-100%;
o: when the pattern is formed, the number of the residual patterns in the coating film after the development is 80-95%;
and (delta): when forming the pattern, the number of the pattern remained in the coating film after the development is less than 80 percent;
TABLE 2
As can be seen from the above table, the compositions having a photosensitive resin required less exposure intensity, higher sensitivity, and better adhesion property to the substrate in forming a pattern, compared to comparative examples 1 and 2. At 60mJ/cm2Can form a pattern excellent in a linear pattern at a low exposure amount; at 40mJ/cm2At such a low exposure amount, the line pattern of 10 μm also has strong adhesion to the substrate, and particularly, the comparison of examples 3,5, 7 and 8 with comparative examples 1 and 2 further shows the excellent linearity and adhesion of the photocurable resin composition provided by the present invention. In addition, the difference between the results of examples 1 and 2 is that the addition of carbon black contributes to the filling of the gap of the organic matter curing, and the smoothness is improved.
Alkali solubility test:
the residual film rate of the development is measured by the over-development of the composition in the above examples, and the alkali-resistant solubility is judged by the residual film rate. The higher the developing residual film rate, the stronger the alkali solvent resistance. The results are shown in table 3.
TABLE 3
As can be seen from the above table, the comparative results of the data of the developing residual film rate show that the developing residual film rate in the examples containing the photosensitive resin composition of the present application is significantly higher than that in the comparative examples, which indicates that the alkali-resistant solubility of the photosensitive composition of the present application is better.
Evaluation of chemical resistance
The developed substrate was baked at 90 ℃ for 60min, measured with a film thickness meter to obtain the thickness of the pattern, immersed in an organic glass solvent at 60 ℃ for 2min, dried again, and then the film thickness was remeasured to evaluate the chemical resistance according to the following criteria. The results are shown in Table 4.
Evaluation criteria
Very good: before and after the stripping treatment, the film thickness change is less than 1%;
o: before and after stripping treatment, the film thickness changes by 1-3%;
and (delta): before and after stripping treatment, the film thickness changes by 3-5%;
TABLE 4
As can be seen from the above table, the composition examples provided by the present invention have better solvent resistance than comparative examples 1 and 2, especially better solvent resistance than examples 6 to 9, 11 and 13.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
compared with the carboxylic acid group content of the conventional similar photosensitive resin in the prior art, the carboxylic acid group content of the photosensitive resin with the structural formula I is less, and the content of active groups such as side chain alcoholic hydroxyl groups or epoxy groups is increased, so that the acid value of the photosensitive resin is further reduced, the reaction activity and the curing performance are improved, and the photocuring performance, the adhesion to a substrate, the alkali solubility and the solvent resistance of the obtained modified photosensitive resin are further improved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. A photocurable resin composition comprising a photosensitive resin, an initiator, and a photopolymerizable monomer, wherein the photosensitive resin has the following structural formula I:
structural formula I
In the structural formula I, R1Is hydrogen or methyl; m is1、m2、n1And n2Each independently is 0 or 1; r is2Is C1~C5Straight chain alkyl or C3~C5Any one of the branched alkyl groups of (a); r5And R6Is one of H and isobutyl; r is3、R4、R5And R6At least one of the groups is H, and all the groups are not H at the same time; A. b independently represents a substituent group, n is any one integer of 1 to 20,
R3、R4independently selected from any one of the following groups: H.
、
、
、
、
、
、
、
、
、
denotes the position of the linking ester group,
a is
Denotes the linking position of an acid anhydride,
b is
Denotes the attachment position of the acid anhydride,
the acid value of the photosensitive resin is 1-130 mgKOH/g.
2. The photocurable resin composition according to claim 1, wherein the acid value of the photosensitive resin is 70 to 120 mgKOH/g.
3. The photocurable resin composition according to claim 1, wherein the photosensitive resin is 20 to 50 parts by mass, the initiator is 0.1 to 10 parts by mass, and the photopolymerizable monomer is 1 to 25 parts by mass.
4. The photocurable resin composition according to claim 3, wherein the amount of the photosensitive resin is 25 to 35 parts by mass.
5. The photocurable resin composition according to claim 3, wherein the amount of the initiator is 0.5 to 5 parts by mass.
6. The photocurable resin composition according to claim 3, wherein the photopolymerizable monomer is present in an amount of 10 to 20 parts by mass.
7. The photocurable resin composition of claim 1, wherein the initiator is one or more selected from the group consisting of benzophenone-based initiators, triazine-based initiators, dialkoxyphenyl acetophenones-based initiators, α -hydroxyalkyl phenones-based initiators, α -aminoalkylphenones-based initiators, acylphosphine oxide-based initiators, benzoin-based initiators, benzil-based initiators, heterocyclic arone-based initiators, and oxime ester-based photoinitiators.
8. The photocurable resin composition according to claim 3 or 7, wherein said photocurable resin composition further comprises a colorant.
9. The photocurable resin composition according to claim 8, wherein the colorant is present in an amount of 1 to 10 parts by mass.
10. The photocurable resin composition according to claim 8, wherein the colorant is present in an amount of 1 to 5 parts by mass.
11. The photocurable resin composition according to claim 3 or 7, wherein said photocurable resin composition further comprises a solvent.
12. The photocurable resin composition according to claim 11, wherein the solvent is added in an amount such that the photocurable resin composition has a solid content of 1-55 wt%.
13. The photocurable resin composition according to claim 11, wherein the solvent is added in an amount such that the photocurable resin composition has a solid content of 30-55 wt%.
14. An optical filter produced from a photocurable resin composition, wherein the photocurable resin composition is the photocurable resin composition according to any one of claims 1 to 13.
15. A photoresist comprising a photocurable resin composition, wherein the photocurable resin composition is the photocurable resin composition according to any one of claims 1 to 13.
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| CN101591423A (en) * | 2008-05-29 | 2009-12-02 | 新日铁化学株式会社 | Alkali soluble resin and manufacture method thereof and the photosensitive polymer combination, cured article and the colour filter that have used alkali soluble resin |
| KR20120013396A (en) * | 2009-04-27 | 2012-02-14 | 닛산 가가쿠 고교 가부시키 가이샤 | Photosensitive composition utilizing photopolymerizable polymer having fluorene skeleton |
| CN106397752A (en) * | 2016-10-14 | 2017-02-15 | 常州强力电子新材料股份有限公司 | Fluorene-containing photosensitive resin, preparation method thereof as well as photocuring composition and photoresist containing photosensitive resin |
| CN110066391A (en) * | 2018-01-24 | 2019-07-30 | 常州强力先端电子材料有限公司 | Modified photosensitive resin and its application |
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| CN101591423A (en) * | 2008-05-29 | 2009-12-02 | 新日铁化学株式会社 | Alkali soluble resin and manufacture method thereof and the photosensitive polymer combination, cured article and the colour filter that have used alkali soluble resin |
| KR20120013396A (en) * | 2009-04-27 | 2012-02-14 | 닛산 가가쿠 고교 가부시키 가이샤 | Photosensitive composition utilizing photopolymerizable polymer having fluorene skeleton |
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