WO2021078230A1 - Photo-curing resin, photo-curing resin composition and black matrix material - Google Patents

Abstract

Provided are a photo-curing resin, a photo-curing resin composition and a black matrix material. The photo-curing resin has the following structure: (I), wherein R₁ is any one of a C₆-C₂₀ cycloalkyl and a C₆-C₂₀ aryl; R₂, R₃, R₄, and R₅ are each independently any one of H, a C₁-C₁₀ alkyl, a C₃-C₂₀ cycloalkyl, and a C₆-C₂₀ aryl; and R₆ has a structure as represented by -R₇-Si-(R₈)n₁(OR₉)n₂, wherein R₇ is any one of a C₁-C₁₀ alkylene and a C₁-C₁₅ alkylenealkoxy, each R₈ is independently any one of a C₁-C₁₀ alkyl and a C₁-C₁₅alkoxy, and each R₉ is independently any one of hydrogen and a C₁-C₁₀ alkyl. When the above photo-curing resin is used in combination with an alkali-soluble resin, a film layer structure having a high substrate adhesion, a good resistance to alkali dissolution and a good heat resistance can be formed.

Description

Light curing resin, light curing resin composition and black matrix material Technical field

The invention relates to the field of light-curing resins, and in particular to a light-curing resin and a black matrix material of a light-curing resin composition.

Background technique

In recent years, flat-panel displays need to use bright backlights as the display area continues to expand. As the backlight becomes brighter, the requirements for the black matrix's light-shielding performance and the fineness of development are getting higher and higher. In order to improve the light-shielding and contrast of the black matrix, methods of increasing the pigment content are often used. As the pigment content increases, the adhesion of the black matrix to the substrate becomes weaker, and the alkali solubility and heat resistance are affected to varying degrees. The Japanese Patent Publication No. JP2006259716A adds a difunctional reactive monomer to a photosensitive resin composition to increase the degree of crosslinking of the photosensitive resin composition during exposure to form a black matrix with a high-definition pattern.

Polymer compounds with a fluorene skeleton have excellent properties such as high heat resistance, high transparency, high refractive index, and low expansion coefficient. For example, the Chinese patent with the authorized announcement number CN100564349C and the Chinese patent application with the publication number CN101965375A respectively disclose: Containing a fluorene skeleton polymer compound, it can solve the problem of high refractive index and heat resistance of traditional photo-curable resin composition to a certain extent, but the film layer formed by the obtained photo-curable resin composition has adhesion to the substrate and alkali resistance Solubility, solvent resistance, etc. are difficult to meet the requirements. The Chinese patent application with publication number CN109343308A discloses a siloxane-modified acrylate composition whose coating film has a significantly improved resistance to acid, but there is no clear description of alkali resistance and so on. The Chinese patent application with publication number CN103718107A discloses a composition containing a silane-modified resin, which has certain deficiencies in alkali solubility, heat resistance, etc., although the adhesion to the developed pattern is improved to a certain extent.

Summary of the invention

The main purpose of the present invention is to provide a photocurable resin, a photocurable resin composition and a black matrix material to solve the problem that the photocurable resin in the prior art cannot have both alkali resistance and heat resistance at the same time during application. .

In order to achieve the above objective, according to one aspect of the present invention, a light-curing resin is provided, the light-curing resin having a structure represented by structural formula I:

Wherein, R ₁ represents any one of a C ₆ ～C ₂₀ cycloalkyl group or a C ₆ ～C ₂₀ aryl group; R ₂ , R ₃ , R ₄ , and R _{5 are the} same or different, and R ₂ , R ₃ , R ₄ and R ₅ each independently represent any of H, C ₁ ～C ₁₀ alkyl, C ₃ ～C ₂₀ cycloalkyl, C ₆ ～C ₂₀ aryl; R ₆ has -R _{The structure represented by 7} -Si-(R ₈ )n ₁ (OR ₉ )n ₂ , R ₇ represents any one of C ₁ ～C ₁₀ alkylene or C ₁ ～C ₁₅ alkylene alkoxy , Each R ₈ each independently represents any one of a C ₁ ～C ₁₀ alkyl group or a C ₁ ～C ₁₅ alkoxy group, and each R ₉ each independently represents hydrogen, in a C ₁ ～C ₁₀ alkyl group In the case of multiple _{R 8} or R _{9 , each R 8 is the} same or different, each R _{9 is the} same or different, n ₁ and n ₂ are positive integers and n ₁ +n ₂ =3; x , Y, z, n each independently represent an integer, and x and n are not 0.

Furthermore, the above-mentioned R ₁ represents any one of a _{C 6} -C ₁₂ cycloalkyl group and a C ₆ -C _{12 aromatic group.}

Further, the above-mentioned R ₂ , R ₃ , R ₄ , and R _{5 are the} same, and preferably R ₂ , R ₃ , R ₄ , and R ₅ are any one of H, methyl, isopropyl, cyclohexyl, phenyl and benzyl Kind.

Further, in the above-mentioned R ₆ , R ₇ represents any one of a C ₁ to C ₅ alkylene group or a C ₁ to C ₁₀ alkylene alkoxy group, preferably a C ₁ to C ₅ alkyl group, C _{Any one of 3} to C ₅ alkylene alkoxy; n ₁ is 2, n ₂ is 1, and each R ₈ represents a C ₁ to C ₅ alkyl group, in the C ₁ to C ₁₀ alkoxy group _{R 9} represents any one of _{C 1} ～C ₅ alkyl group, C ₁ ～C ₁₀ alkoxy group, preferably C ₁ ～C ₅ alkyl group, C ₁ ～C ₅ alkoxy group Any of the bases.

Furthermore, the weight average molecular weight of the above-mentioned photocurable resin is 5000-15000, more preferably 6000-10000.

According to another aspect of the present invention, there is provided a photocurable resin composition, comprising a photocurable acrylate resin, an alkali-soluble resin, a photopolymerizable monomer and an initiator, and the photocurable acrylate resin is any one of the above Kind of light-curing resin.

Further, the above-mentioned alkali-soluble resin has the following structural formula:

Among them, A and B are substituents, and n ₃ is any integer of 1-20.

Further, the above A is selected from any one of the following groups:

* Indicates the possible connection position of acid anhydride;

Further, the above-mentioned B is selected from any one of the following groups:

* Indicates the possible attachment positions of acid anhydrides.

Further, the total mass parts of the photocurable acrylate resin and the alkali-soluble resin is 10-50 parts by mass, preferably the total mass parts of the photocurable acrylate resin and the alkali-soluble resin is 20-30 parts by mass, and the photocurable The mass ratio of acrylic resin to alkali-soluble resin is 7:10-8:10; the photopolymerizable monomer is 1-30 parts by mass, more preferably 15-25 parts by mass; the photopolymerization initiator is 1-5 parts by mass, More preferably, it is 1 to 3 parts by mass.

Furthermore, the above-mentioned photocurable resin composition further includes a coloring agent, and the coloring agent is 30-60 parts by mass, preferably 40-50 parts by mass.

According to another aspect of the present invention, there is provided a black matrix material, including a photocurable resin composition, the photocurable resin composition of which is any one of the above-mentioned photocurable resin compositions.

Applying the technical solution of the present invention, the photocurable resin with structural formula I suspended the silane group as a side chain group on the polymer main chain. When used in conjunction with alkali-soluble resins in the art, it can form a high substrate adhesion, Film structure with good alkali resistance and good heat resistance.

Detailed ways

It should be noted that the embodiments in this application and the features in the embodiments can be combined with each other if there is no conflict. Hereinafter, the present invention will be described in detail with reference to the embodiments.

As analyzed in the background art of this application, the prior art photocurable resin cannot have both alkali resistance and heat resistance at the same time when applied. In order to solve this problem, the present application provides a photocurable resin and a photocurable resin. Composition, photoresist and black matrix material.

In a typical implementation of the present application, a light-curing resin is provided, and the light-curing resin has a structure represented by structural formula I:

Wherein, R ₁ represents any one of a C ₆ ～C ₂₀ cycloalkyl group or a C ₆ ～C ₂₀ aryl group; R ₂ , R ₃ , R ₄ , and R _{5 are the} same or different, and R ₂ , R ₃ , R ₄ and R ₅ each independently represent any of H, C ₁ ～C ₁₀ alkyl, C ₃ ～C ₂₀ cycloalkyl, C ₆ ～C ₂₀ aryl; R ₆ has -R _{The structure represented by 7} -Si-(R ₈ )n ₁ (OR ₉ )n ₂ , R ₇ represents any one of C ₁ ～C ₁₀ alkylene or C ₁ ～C ₁₅ alkylene alkoxy , Each R ₈ each independently represents any one of a C ₁ ～C ₁₀ alkyl group or a C ₁ ～C ₁₅ alkoxy group, and each R ₉ each independently represents hydrogen, in a C ₁ ～C ₁₀ alkyl group In the case of multiple _{R 8} or R _{9 , each R 8 is the} same or different, each R _{9 is the} same or different, n ₁ and n ₂ are positive integers and n ₁ +n ₂ =3; x , Y, z, n each independently represent an integer, and x and n are not 0.

The photocurable resin with structural formula I of the present invention has silane groups as side chain groups suspended on the polymer main chain. When used in conjunction with alkali-soluble resins in the field, it can form a substrate with high adhesion and good alkali solubility. , Film structure with good heat resistance.

In order to improve the hardness and heat resistance of the resin, it is preferable that the above-mentioned R ₁ represents any one of a C ₆ -C ₁₂ cycloalkyl group or a C ₆ -C ₁₂ aromatic group, and more preferably a cyclohexyl group, a phenyl group, or a benzyl group. Compared with monomers with other macrocyclic groups, monomers containing these groups have easier raw materials to obtain, and the hardness and heat resistance can also meet the requirements.

In order to improve the stability of structural formula I and the efficiency of synthesis, it is preferable that the above R ₂ , R ₃ , R ₄ , and R _{5 are the} same, and it is more preferable that R ₂ , R ₃ , R ₄ , and R ₅ are H, methyl, or isopropyl. Any one of phenyl, cyclohexyl, phenyl and benzyl.

In order to improve the heat resistance of the resin, the adhesion of the substrate, and the efficiency of synthesis, it is preferable that in the above-mentioned R ₆ , R ₇ represents any of a C ₁ to C ₅ alkylene group or a C ₁ to C ₁₀ alkylene alkoxy group. One kind, preferably any one of a C ₁ ～C ₅ alkyl group and a C ₃ ～C ₅ alkylene alkoxy group, more preferably R ₇ represents a methylene group or a methoxymethylene group; n ₁ Is 2, n ₂ is 1, each R ₈ represents a C ₁ ～C ₅ alkyl group, _{any one of C 1} ～C ₁₀ alkoxy group, preferably each R ₈ represents H, methyl, ethyl, Any one of a methoxy group and an ethoxy group, R ₉ represents a C ₁ -C ₅ alkyl group or a C ₁ -C ₁₀ alkoxy group. Either one, preferably a C ₁ -C ₅ alkane group, any one of C ₁ ~ C ₅ alkoxy group, more preferably R ₉ represents H, methyl, ethyl, methoxy, ethoxy any one of.

In an embodiment of the present application, in order to increase the curing rate of the photocurable resin, the weight average molecular weight of the photocurable resin is preferably 5000-15000, more preferably 6000-10000.

In another exemplary embodiment of the present application, a photocurable resin composition is provided, which includes a photocurable acrylate resin, an alkali-soluble resin, a photopolymerizable monomer, an initiator, and a solvent. The photocurable acrylate The similar resin is any one of the above-mentioned photocurable resins.

The photocurable resin with structural formula I of the present invention has silane groups as side chain groups suspended on the polymer main chain. When used in conjunction with alkali-soluble resins in the field, it can form a substrate with high adhesion and good alkali solubility. , Film structure with good heat resistance.

Alkali-soluble resins in the prior art can be considered to be used in conjunction with the above-mentioned photocurable resins of the present application, preferably alkali-soluble resins containing fluorene groups, and more preferably the above-mentioned alkali-soluble resins have the following structural formula

Among them, A and B are substituents, and n ₃ is any integer of 1-20.

The content of carboxylic acid groups of the above-mentioned alkali-soluble resins is less than that of conventional alkali-soluble resins of the same kind in the prior art, and the content of active groups such as side-chain alcoholic hydroxyl groups is increased, which further reduces the photosensitive resin The acid value improves the reactivity and curing rate, so that the photocuring performance, adhesion to the substrate, alkali and solvent resistance, and solvent resistance of the composition are further improved.

The substituent group represented by A in the above structural formula can theoretically be any chemically acceptable group. In order to further optimize the advantages of the photosensitive resin, it is preferable that A is selected from any one of the following groups:

* Indicates the possible attachment positions of acid anhydrides.

The substituent group represented by B in the above structural formula can theoretically be any chemically acceptable group. In order to make the performance of the above photosensitive resin more stable, it is preferable that B is selected from any one of the following groups:

* Indicates the possible attachment positions of acid anhydrides.

In order to make full use of the advantages of the above-mentioned resins, the total mass parts of the light-curable acrylic resin and the alkali-soluble resin is 10-50 parts by mass, preferably the total mass parts of the photo-curable acrylic resin and the alkali-soluble resin is 20~ 30 parts by mass, and the mass ratio of the photocurable acrylate resin and the alkali-soluble resin is 7:10-8:10.

In an embodiment, the above-mentioned photopolymerizable monomer is 1-30 parts by mass, more preferably 15-25 parts by mass. The photopolymerizable monomer used in the above-mentioned photocurable resin composition is used to improve the photosensitivity, mechanical strength, crosslinkability, chemical resistance and other properties of the photocurable resin composition. As the polymerizable monomer, as long as the compound has one or more unsaturated bonds in the molecule, one or a combination of several of them can be selected as required. Illustrative examples of the photopolymerizable monomer selected in the present invention are propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. (Meth)acrylic acid adducts of epoxy compounds such as ether, sorbitol triglycidyl ether, glycerol triglycidyl ether; unsaturated organic acids such as maleic acid and their anhydrides; N-methacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-methylolacrylamide, N-methacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N -Methylolmethacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylmethyl Acrylamides such as acrylamide; polyethylene glycol di(meth)acrylate (the number of ethylene groups is 2-14); trimethylolpropane di(meth)acrylate, trimethylolpropane tri(methyl) ) Acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane propoxy tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, four Hydroxymethylmethane tetra(meth)acrylate, polypropylene glycol di(meth)acrylate (propylene number is 2-14); dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate , Bisphenol A polyoxyethylene di(meth)acrylate, bisphenol A dioxyethylene di(meth)acrylate, bisphenol A trioxyethylene di(meth)acrylate, bisphenol A oxyethylene di(meth)acrylate (Meth) acrylates, polycarboxylic acids (such as phthalic anhydride, etc.) and compounds with hydroxyl and ethylenically unsaturated groups (such as (meth) acrylate β-hydroxyethyl, etc.) Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.; ethylene glycol dishrink Glyceryl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, styrene, hydroxystyrene and other styrenes; N -Vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylimidazole, etc.; each of the substances listed above can be used alone or in combination.

In an embodiment, the photopolymerization initiator is preferably 1 to 5 parts by mass, preferably 1 to 3 parts by mass. The initiator in the above-mentioned photocurable resin composition is mixed in a state of being dissolved or dispersed in a solvent. The initiator used in the present invention is not particularly limited, and can be selected from benzophenone-based initiators, triazine-based initiators, dialkoxyacetophenone-based initiators, α-hydroxyalkylphenone-based initiators, α-Amino alkyl phenone initiators, acyl phosphine oxide initiators, benzophenone initiators, benzoin initiators, benzyl initiators, heterocyclic aromatic ketone initiators, oxime esters One or more combinations of photoinitiators. Particularly preferred are oxime ester initiators. Exemplary examples are: benzophenone, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, diethoxyacetophenone, 2,4-bis (Trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5 -Triazine, benzoin, benzoin methyl ether, benzoin isobutyl ether, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethoxyanthracene, 10-butyl -2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, o-ethoxycarbonyl-a-oxyimino-1-phenylpropanone, 1,2-octanedione, 1 -(4-phenylthio)phenyl-2 (o-benzoyl oxime), 1-(9-ethyl)-6-(2-methylbenzoyl)carbazol-3-yl-1-(O -Acetyl oxime), OXE-01, NCI-831, 2,4,5-triarylimidazole dimer, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzene Methyl ketone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, trichloroacetophenone, pentyl-4-dimethylaminobenzoate, 9-benzene Acridine, 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- 2Methylphenyl)vinyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-(2-bromo-4-methoxy Yl)phenyl-s-triazine, 2,4-bis(trichloromethyl)-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4- Bis(trichloromethyl)-6-(2-bromo-4-methoxy)styrene phenyl-s-triazine, 4-benzoyl-4'-methyl dimethyl sulfide, 4- Ethyl dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedi One or a mixture of ketone-2 (o-ethoxycarbonyl) oxime and other compounds.

When the photocurable resin composition of the present invention is used in applications such as filter preparation, a solvent for dispersion is required. As a common solvent, (poly)alkylene glycol monoalkyl ethers can be selected, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, di Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether 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.; Aromatic hydrocarbons, such as: toluene, xylene, trimethylbenzene, etc.; amide compounds, such as: N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc.; carboxylate Acid ester compounds, such as: ethyl 2-oxobutyrate, methyl acetoacetate, ethyl acetoacetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, formic acid N-pentyl ester, isoamyl acetate, butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl acetone , Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl- 3-Methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, etc.; similar solvents, such as: methyl ethyl ketone, cyclohexanone, heptanone, 3-heptanone, etc.; cyclic ether Compounds, such as tetrahydrofuran and pyran; cyclic ester compounds, such as γ-butyrolactone. The above organic solvents can be used alone or in a mixture of two or more, among which propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol Solvents such as monomethyl ether and diethylene glycol methyl ethyl ether have good solubility for the photosensitive resin composition of the present invention; further preferred solvents are propylene glycol monomethyl ether acetate and diethylene glycol methyl ethyl ether. Preferably, the amount of the solvent added is such that the solid content of the photocurable resin composition is 10-50% by weight, more preferably 15-40% by weight.

According to product application requirements, the above-mentioned photocurable resin composition can optionally be added with colorants commonly used in the art, and color filters can be well formed by adding colorants.

Any organic pigments and inorganic pigments commonly used in the art can be selectively used as the colorant in this application. These include water-soluble pigments, water-insoluble azo pigments, phthalocyanine pigments, acridone pigments, isoindoline pigments, indolanthrone pigments, indanthrone pigments, diketopyrrole pigments, etc. The above-mentioned pigments can be used alone or mixed, depending on the specific requirements of the product.

Organic raw materials are more preferable, and specific pigments are exemplified as follows, but are not limited to the following pigments. Specific examples of compounds with color index (The Society of Dyers and Colourists) (C.I.) serial number are as follows:

C.I. Pigment Black 1 and 7 etc.

When the colorant is used as a light-shielding agent, it is preferable to use a black pigment. Examples of the black pigment include metal oxides, composite oxides, metal sulfides, and metals such as carbon black, titanium black, copper, iron, and manganese. Sulfate, metal carbonate, etc. Among them, carbon black having high light-shielding properties is preferable. The content of the coloring agent may be appropriately determined according to the use of the photosensitive resin composition, and is preferably 30 to 60 parts by mass, and more preferably 40 to 50 parts by mass. In order to uniformly disperse the colorant in the photocurable resin composition, a dispersant may also be used. As such a dispersing agent, polyethyleneimine-based, polyurethane resin-based, acrylic resin-based polymer dispersing agents, particularly oleic acrylic resin-based dispersing agents are preferably used.

When the photocurable resin composition contains the above-mentioned photocurable acrylate resin, alkali-soluble resin, photopolymerizable monomer, initiator, colorant and solvent, the total mass of the photocurable resin composition is calculated as 100 parts by mass : The total mass parts of the photocurable acrylic resin and the alkali-soluble resin is 10-50 parts by mass, preferably 20-30 parts by mass; the colorant is 20-60 parts by mass, preferably 30-40 parts by mass; the photopolymerizable monomer is 1 to 30 parts by mass, preferably 15 to 25 parts by mass; photopolymerization initiator is 1 to 5 parts by mass, preferably 1 to 3 parts by mass; solvent is 10 to 50 parts by mass, preferably 15 to 40 parts by mass.

In another preferred embodiment of the present invention, the above-mentioned photocurable resin composition may contain additives, such as fillers, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, etc., but are not limited to this.

Among them, the curing agent is used to improve the deep curing performance and mechanical strength. The curing agent can be specifically selected from epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds, but is not limited to these compounds. The leveling agent can use commercially available surfactants, which can specifically include silicone surfactants, ester surfactants, ionic surfactants, nonionic surfactants, amphoteric surfactants, etc., which are surface active. The agent can be used alone or in combination of two or more. The adhesion promoter can use silane compounds, and specific examples include: vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tris (2-methoxyethoxy) silane, N-(2- Aminoethyl)-30 aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. The above-mentioned adhesion promoters may be used alone or in combination of two or more kinds. Specific examples of antioxidants include: 4,4'-butylene bis(6-tert-butyl-3-methylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,3'- Thiobis(4-methyl-6-tert-butylphenol), p-methoxyphenol, etc. The ultraviolet absorber can be 2-(3-tert-butyl-2hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone and the like.

In another exemplary embodiment of the present application, a black matrix material is provided, including a photocurable resin composition, and the photocurable resin composition is any one of the above-mentioned photocurable resin compositions. Since the photocurable resin composition of the present application has strong adhesion, alkali solubility and high temperature resistance, the adhesion of the formed black matrix has the above advantages.

The synthetic route of the above-mentioned photocurable resin is to obtain organosilane-modified acrylic by reacting with a carboxyl-containing acrylic copolymer resin through a silane coupling agent containing epoxy, hydroxyl and other active substituent groups in the presence of a catalyst Resin, that is, the light-curable resin of the present application. The synthesis method of the photocurable resin is illustrated below with an example.

Synthesis Example 1

In a 500ml four-necked flask equipped with a stirring device, a condenser, a constant pressure dropping funnel, a thermometer and a nitrogen inlet, add 100g of propylene glycol methyl ether acetate (PGMEA), fill with nitrogen, and heat to 70°C under stirring. Drop the monomer mixture (see Table 1 for the formula) and the initiator (azobis-isoheptanonitrile) solution, and control the dripping time at 2h. After the dripping is completed, keep it at this temperature for 4h. After the Mw of the measuring system reaches the requirement, Acrylic resin is obtained when the temperature is lowered. According to different monomer combinations, acrylic resins 1-5 and comparative resins were prepared respectively, and the specific formulas are shown in Table 1.

Table 1

Synthesis Example 2

Add a certain amount of the above acrylic resin 1 into a 500ml reaction four-neck flask, heat it to 110°C, after the system temperature stabilizes, add 0.5% (relative to the resin mass) of tetrabutylammonium bromide and silane coupling agent 3-( 2,3-Glyoxypropoxy)propyltriethoxysilane (containing epoxy group), the epoxy equivalent of the system is measured after the temperature is maintained at 110°C for 2h. When the epoxy equivalent is greater than 25000g/mol, the reaction is stopped and the temperature is lowered. , Discharge and seal to obtain organosilane modified acrylic resin 1, namely modified resin 1.

Using the above method, the acrylic resins 2 to 5 are modified with a silane coupling agent to prepare silane-modified acrylic resins 2 to 15. The specific silane coupling agent and modified resin are shown in Tables 2 to 4 below.

Synthetic comparative example 1 (comparative example resin 1)

Add a certain amount of the above-mentioned comparative resin prepolymer into a 500ml reaction four-neck flask, heat it to 110°C, after the system temperature stabilizes, add 0.5% (relative to the resin mass) of tetrabutylammonium bromide and glycidyl methacrylate Ether (GMA), heat preservation and reaction at 110°C for 2h, start to test the epoxy equivalent of the system. When the epoxy equivalent is greater than 25000g/mol, stop the reaction, cool down, discharge and seal, and then obtain the comparative resin 1.

Table 2

table 3

Table 4

Evaluation of light-curable resin composition

1. Preparation of light-curable resin composition for simple evaluation

An exemplary photocurable resin composition was prepared, and the application performance of the organosilane modified resin given in the examples of the present invention was evaluated. Preferably, the modified resin prepared in the above-mentioned embodiments is tested and compared. With reference to the formulations shown in Examples 1-15 and Comparative Examples 1-2 in Table 5, the raw materials were uniformly mixed in the following proportions to form a photocurable resin composition.

Among them, the light-curing resin is mixed with part of the solvent first, and then mixed with other components.

table 5

Note: The structural formula of alkali-soluble resin II selected here is shown in the figure below:

Different ratios of modified resin 1 and alkali-soluble resin II were selected, and the photocurable resin compositions of Examples 16 to 20 were prepared according to the mass ratio in Table 5, and the corresponding photopolymerizable monomers, initiators, colorants, and The solvent is the same as in Example 1, for comparison, and specific examples are shown in Table 6.

Table 6

2. Application performance evaluation of light-curable resin composition

Using a spin coater, the photocurable resin compositions of Examples 1-20 and Comparative Examples 1 and 2 were coated on a glass substrate (100mm×100mm), and pre-baked at 90°C for 90 seconds to form a film thickness 1.0μm coating film. Then, a mirror projection was used to align the exposure device, the exposure gap was set to 50 μm, and a negative image mask having a linear pattern of 20 μm was used to expose and isolate the exposure. The exposure intensity was set to 4 levels of 20, 40, 60, and 120mJ/cm ^2. The exposed sample film was developed in a 0.04% by mass KOH aqueous solution at 26°C for 40s, 60s, and 80s, and then baked at 230°C for 30 minutes to form a linear pattern. The pattern characteristics and the residual rate of film formation were tested. Test its alkali solubility, solvent resistance and other properties.

Similarly, the coating film was irradiated with ultraviolet rays with an exposure gap of 50 μm through a negative image mask formed with linear patterns of 2, 5, 10, and 20 μm. The exposure amount is set to 20mJ/cm ² . After the exposed coating film was developed in a 0.04% by mass KOH aqueous solution at 26°C, post-baking was performed at 230°C for 30 minutes to form a linear pattern. The formed pattern was observed with an optical microscope, and the linearity and adhesion of the pattern were evaluated. The specific evaluation situation is shown in Table 7 below. In addition, the application effect of the photoresist resin composition containing the modified resin 1 and the alkali-soluble resin II in different proportions was evaluated, and the specific evaluation conditions are shown in Table 8.

evaluation standard:

Pattern linearity:

○: There is no jagged edge on the pattern line;

△: The edge of the pattern line is jagged.

Adhesion between pattern and substrate:

○Not peeled off from the substrate, forming a linear pattern;

△ Although a linear pattern is formed, there is a pattern defect;

╳ Peel off from the substrate without forming a linear pattern.

Table 7

Table 8

The above test results show, Example 2, Example 5, Example 9, Example 10, Example 13, Example 14 and the like, at 40mJ / cm ² exposure, have demonstrated good linearity, 60mJ / The ^{examples all showed good linearity at cm 2} exposure, while the linearity of the comparative example was not good, and there were jagged edges. The adhesion test showed that the 2μm linear pattern, Examples 1-15 have shown certain adhesion; the 5μm-10μm line width pattern has obviously better adhesion, while the comparative example has peeling off in the 2μm linear pattern , 10μm linear pattern also has obvious defects.

In comparison of the linearity of Examples 16-20, the 40mJ exposure energy condition is small, and the linearity of Example 18 is better, while the linearity of Example 16, Example 17, Example 19, and Example 20 is slightly insufficient; , With a linear pattern of 5 μm, Example 17, Example 18, and Example 19 all showed good adhesion, while the adhesion of Example 16 and Example 20 was significantly lower. Therefore, it can be seen from a comprehensive comparison that the ratio of the two resins in Example 18 is a relatively suitable ratio. In other embodiments, this ratio is used for application performance testing.

Evaluation of heat resistance and alkali resistance:

The coating film was irradiated with ultraviolet rays with an exposure gap of 50 μm through a negative image mask formed with linear patterns of 2, 5, 10, and 20 μm. The exposure amount is set to 20mJ/cm ² . After the exposed coating film was developed in a 0.04% by mass KOH aqueous solution at 26°C, post-baking was performed at 230°C for 30 minutes to form a linear pattern. The formed pattern was observed with an optical microscope, the heat resistance (the contact angle between the pattern edge and the substrate) and the alkali solubility were evaluated, and the determination was made from the measurement result of the residual film rate. The specific evaluation situation is shown in Table 9 below. In addition, the above-mentioned photocurable resin compositions containing modified resin 1 and alkali-soluble resin II in different proportions were compared, and a better resin ratio was selected. The specific comparison results are shown in Table 10.

The evaluation criteria are as follows

Alkali resistance

○Remaining film rate≥95%

△95%＞The residual film rate≥90%

╳Remaining film rate <90%

Heat resistance

○The contact angle between the pattern edge and the substrate>45°

△The contact angle between the pattern edge and the substrate is 40°-45°

╳The contact angle between the pattern edge and the substrate <40°

Table 9

Table 10

From the above test results, it can be seen that the photocurable resin compositions corresponding to Examples 1-15 all have good alkali resistance; after 230°C post-baking, the contact angles between the edges of the resulting patterns and the substrate are all >45°, The heat resistance is better, and the contact angles of the comparative examples are all <40°C, and the heat resistance is relatively poor.

In addition, a comparison of the above-mentioned photocurable resin composition containing modified resin 1 and alkali-soluble resin II in different proportions shows that Example 17, Example 18, Example 19, etc. all have good alkali solubility resistance. And heat resistance, especially Example 18 has excellent alkali solubility and heat resistance. Therefore, the ratio of modified resin and alkali-soluble resin II corresponding to Example 18 is a relatively good ratio condition. Other comparative examples All refer to this ratio for the preparation and application evaluation of the composition.

In summary, the organic silane-modified photocurable resin and its composition provided by the present invention have excellent application performance, better heat resistance, better linearity and adhesion, and have broad application prospects.

From the above description, the above-mentioned embodiments of the present invention achieve the following technical effects:

In this application, the photocurable resin composition prepared by using the photosensitive resin with the above-mentioned specific structural formula I and the alkali-soluble resin in combination has good linearity in development, good adhesion to the substrate, and good post-baking heat resistance. Good alkali resistance and solubility.

The above descriptions are only preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (11)

1. A light-curing resin, characterized in that the light-curing resin has a structure represented by structural formula I:

   

   Wherein, R ₁ represents any one of a C ₆ ～C ₂₀ cycloalkyl group or a C ₆ ～C ₂₀ aryl group;

   R ₂ , R ₃ , R ₄ , and R _{5 are the} same or different, and R ₂ , R ₃ , R ₄ , and R ₅ each independently represent H, C ₁ ～C ₁₀ alkyl, C ₃ ～C ₂₀ cycloalkane Any one of aryl groups, C ₆ ～C _{20 aryl groups;}

   R ₆ has a structure represented by -R ₇ -Si-(R ₈ )n ₁ (OR ₉ )n ₂ , R ₇ represents a C ₁ ～C ₁₀ alkylene group, a C ₁ ～C ₁₅ alkylene alkoxy group _{Each R 8} independently represents any one of a _{C 1} to C ₁₀ alkyl group or a C ₁ to C ₁₅ alkoxy group, and each R ₉ independently represents hydrogen, C ₁ to C Any one of the alkyl groups of _{10 , when R 8} or R ₉ is more than one, each R _{8 is the} same or different, each R _{9 is the} same or different, n ₁ and n ₂ are positive integers and n ₁ +n ₂ = 3;

   x, y, z, n each independently represent an integer, and x and n are not zero.
2. The photocurable resin according to claim 1, wherein the R ₁ represents any one of a _{C 6} to C ₁₂ cycloalkyl group and a C ₆ to C _{12 aromatic group.}
3. The photocurable resin according to claim 1, wherein said R ₂ , said R ₃ , said R ₄ , and said R _{5 are the} same, preferably said R ₂ , said R ₃ , and said R _{4. The} R ₅ is any one of H, methyl, isopropyl, cyclohexyl, phenyl and benzyl.
4. The photo-curable resin according to claim 1, wherein said R _6, said R ₇ represents an optionally C ₁ ~ C ₅ alkylene group is, alkylene alkoxy C ₁ ~ C ₁₀ of One, preferably any one of a C ₁ ～C ₅ alkyl group and a C ₃ ～C ₅ alkylene alkoxy group; n ₁ is 2, n ₂ is 1, each of the R ₈ represents C ₁ to C ₅ alkyl group, _{any one of C 1} to C ₁₀ alkoxy group, said R ₉ represents _{any one of C 1} to C ₅ alkyl group or C ₁ to C ₁₀ alkoxy group , preferably C ₁ ~ C ₅ alkyl group, and any one of C ₁ ~ C ₅ alkoxy.
5. The photocurable resin according to claim 1, wherein the weight average molecular weight of the photocurable resin is 5,000 to 15,000, more preferably 6,000 to 10,000.
6. A photocurable resin composition, comprising a photocurable acrylate resin, an alkali-soluble resin, a photopolymerizable monomer and an initiator, characterized in that the photocurable acrylate resin is any one of claims 1 to 5 The light-curable resin described in the item.
7. The photocurable resin composition according to claim 6, wherein the alkali-soluble resin has the following structural formula

   

   Wherein, said A and said B are substituents, and n ₃ is any integer of 1-20.
8. 8. The photocurable resin composition according to claim 7, wherein the A is selected from any one of the following groups:

   

   

   * Indicates the possible connection position of acid anhydride;

   Preferably, the B is selected from any one of the following groups:

   

   

   

   * Indicates the possible attachment positions of acid anhydrides.
9. The photocurable resin composition according to claim 6, wherein the total mass parts of the photocurable acrylate resin and the alkali-soluble resin is 10-50 parts by mass, preferably the photocurable acrylate resin The total mass parts of the resin and the alkali-soluble resin is 20-30 parts by mass, and the mass ratio of the photocurable acrylate resin and the alkali-soluble resin is 7:10-8:10; the photopolymerizable monomer It is 1 to 30 parts by mass, more preferably 15 to 25 parts by mass; the photopolymerization initiator is 1 to 5 parts by mass, more preferably 1 to 3 parts by mass.
10. The photocurable resin composition according to claim 9, wherein the photocurable resin composition further comprises a colorant, and the colorant is 30-60 parts by mass, preferably 40-50 parts by mass.
11. A black matrix material, comprising a photocurable resin composition, characterized in that the photocurable resin composition is the photocurable resin composition according to any one of claims 6 to 10.