阅读说明：本技术 高粘着性正型光刻胶组合物及其合成方法和固化膜 (High-adhesion positive photoresist composition, synthesis method thereof and cured film ) 是由 陈旺 康威 康凯 于 2021-07-15 设计创作，主要内容包括：本发明涉及一种高粘着性正型光刻胶组合物及其合成方法和固化膜,高粘着性正型光刻胶组合物包括有机溶剂和溶解在有机溶剂中的溶质,溶质包括含环氧基团的硅氧烷共聚物、丙烯酸共聚物、1,2-二叠氮醌类化合物和表面活性剂,溶质中含环氧基团的硅氧烷共聚物的重量比例为50-90wt%。本发明的高粘着性正型光刻胶组合物包含硅氧烷共聚物和丙烯酸共聚物,合成固化膜时硅氧烷共聚物和丙烯酸共聚物共同作为粘合剂,该硅氧烷共聚物由(R1)m(R2)n Si(OR3)4-m-n表示的硅烷中的两种以上通过共聚反应得到,提高了光刻胶组合物的粘着性和残膜率,同时,由该光刻胶组合物制成的固化膜,浸没在有机溶剂、酸或碱中或与有机溶剂、酸或碱接触时,有效改善了溶胀或膜与衬底出现分层的问题。(The invention relates to a high-adhesion positive photoresist composition, a synthesis method thereof and a cured film, wherein the high-adhesion positive photoresist composition comprises an organic solvent and a solute dissolved in the organic solvent, the solute comprises an epoxy group-containing siloxane copolymer, an acrylic copolymer, a1, 2-diazidoquinone compound and a surfactant, and the weight proportion of the epoxy group-containing siloxane copolymer in the solute is 50-90 wt%. The high-adhesion positive photoresist composition comprises a siloxane copolymer and an acrylic copolymer, wherein the siloxane copolymer and the acrylic copolymer are jointly used as an adhesive when a cured film is synthesized, the siloxane copolymer is obtained by copolymerization of more than two kinds of silanes represented by (R1) m (R2) n Si (OR3)4-m-n, the adhesion and the residual film rate of the photoresist composition are improved, and meanwhile, when the cured film prepared from the photoresist composition is immersed in an organic solvent, acid OR alkali OR is contacted with the organic solvent, acid OR alkali, the problem of swelling OR delamination of the film and a substrate is effectively solved.)

1. A high-tack positive-tone photoresist composition characterized by: comprises an organic solvent and a solute dissolved in the organic solvent, wherein the solute comprises siloxane copolymer containing epoxy groups, acrylic copolymer, 1, 2-diazidoquinone compound and surfactant, the weight proportion of the siloxane copolymer containing epoxy groups in the solute is 50-90wt%,

the siloxane copolymer containing the epoxy group is obtained by copolymerization of at least two silanes, the molecular formula of the silane is (R1) m (R2) n Si (OR3)4-m-n, wherein m is an integer from 0 to 3, R1 is an organic group containing the epoxy group, n is an integer from 0 to 3, R2 is any one of C1-12 alkyl, C2-10 alkenyl OR C6-15 aryl, and R3 is any one of hydrogen, C1-6 alkyl, C2-6 acyl OR C6-15 aryl.

2. The high-tack positive-working photoresist composition of claim 1, wherein: the siloxane copolymer comprises a condensate of a silane compound and/or a hydrolysate thereof, the silane compound or the hydrolysate thereof being a monofunctional, difunctional, trifunctional or tetrafunctional silane compound, the siloxane copolymer comprising one or more of siloxane structural units of Q-, T-, D-or M-type.

3. The high-tack positive-working photoresist composition of claim 2, wherein: the Q-type siloxane structural unit, which comprises one silicon atom and adjacent four oxygen atoms, is derived from a hydrolysis product of a tetrafunctional silane compound or a silane compound having four hydrolyzable groups;

the T-type siloxane structural unit, which comprises one silicon atom and three adjacent oxygen atoms, is derived from a product of hydrolysis of a trifunctional silane compound or a silane compound having three hydrolyzable groups;

the D-type siloxane structural unit, which comprises one silicon atom and two adjacent oxygen atoms, is derived from a hydrolysis product of a bifunctional silane compound or a silane compound having two hydrolyzable groups;

the M-type siloxane structural unit, which includes one silicon atom and adjacent one oxygen atom, is derived from a hydrolysis product of a monofunctional silane compound or a silane compound having one hydrolyzable group.

4. The high-tack positive-working photoresist composition of claim 1, wherein: the monomers for polymerization of the acrylic copolymer include one or more of unsaturated monocarboxylic acids including (meth) acrylic acid, crotonic acid and alpha-chloroacrylic acid and cinnamic acid, unsaturated dicarboxylic acids and their anhydrides including maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid.

5. The high-tack positive-working photoresist composition of claim 1, wherein: the monomer for polymerization of the acrylic copolymer includes an ethylenically unsaturated compound having an aromatic ring, and the ethylenically unsaturated compound having an aromatic ring includes phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tribromophenyl (meth) acrylate, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, divinylbenzene, and vinylphenol.

6. The high-tack positive-working photoresist composition of claim 1, wherein: the organic solvent comprises diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate and methyl 2-methoxypropionate,

the surfactant is one of a fluorine surfactant, a silicon surfactant and a nonionic surfactant.

7. The high-tack positive-working photoresist composition of claim 1, wherein: the 1, 2-diazido-quinone compound is one or more of an ester of a phenol compound and 1, 2-diazido-quinone-4-sulfonic acid or 1, 2-diazido-quinone-5-sulfonic acid, an ester of a phenol compound and 1, 2-diazido-naphthoquinone-4-sulfonic acid or 1, 2-diazido-naphthoquinone-5-sulfonic acid, a sulfonamide of a phenol compound with a hydroxyl group substituted by an amino group and 1, 2-diazido-quinone-4-sulfonic acid or 1, 2-diazido-quinone-5-sulfonic acid, or a sulfonamide of a phenol compound with a hydroxyl group substituted by an amino group and 1, 2-diazido-naphthoquinone-4-sulfonic acid or 1, 2-diazido-naphthoquinone-5-sulfonic acid.

8. A method for synthesizing a high-tack positive-working photoresist composition as defined in claim 1, wherein: the method comprises the following steps:

step 1: hydrolysis reaction of silane compound: adding at least two silane compounds of the formula (R1) m (R2) n Si (OR3)4-m-n into a reaction vessel, mixing with water, the silicon-oxygen bond of the silane compounds being broken, and the silicon atom being combined with the hydroxyl group of the water atom to form silanol;

step 2: further silanol breaks a silicon-oxygen bond or breaks a hydrogen-oxygen bond;

and step 3: and (3) silane compound polycondensation reaction: the silanol with broken silicon-oxygen bonds and the silanol with broken hydrogen-oxygen bonds are continuously dehydrated and combined to form siloxane polymer;

and 4, step 4: adding a polymerization monomer and an organic solvent into another reaction container and uniformly mixing, wherein the polymerization monomer is an acrylic acid derivative;

and 5: chain initiation process: adding a free radical initiator into the reaction container, wherein the free radical initiator attacks carbon-carbon double bonds of the polymerization monomers, the carbon-carbon double bonds are broken to generate free radicals, active reaction center free radicals are formed, and the free radicals further attack the carbon-carbon double bonds of the polymerization monomers to form more active reaction center free radicals;

step 6: and (3) chain growth process: the active reaction center free radical repeatedly reacts with the carbon-carbon double bond of the acrylic acid derivative to form a macromolecular free radical;

and 7: chain termination process: the free radicals are combined and eliminated pairwise, and the free radicals are combined with each other to form stable acrylic acid copolymer;

and 8: the siloxane copolymer, the acrylic copolymer and the 1, 2-diazidoquinone compound are weighed, dissolved and mixed in an organic solvent, and the solution of the high-viscosity positive photoresist composition with the target solute content is obtained through filtration.

9. The method for synthesizing a high-tack positive photoresist composition according to claim 7, wherein: the exacerbation reaction is carried out at 65-75 ℃, the polycondensation reaction is carried out for 7 hours under the temperature of 20 ℃ by stirring, and the reaction is accelerated by heating and refluxing.

10. A cured film characterized by: the cured film made from the high-tack positive-working photoresist composition of claim 1 by: coating the photoresist composition on a substrate, prebaking to remove the organic solvent, exposing with a photomask, developing with a developer, baking and curing.

Technical Field

The invention relates to a high-adhesiveness positive photoresist composition, a synthetic method thereof and a cured film.

Background

An LCD or OLED having higher accuracy and resolution characteristics can be manufactured by a method of increasing an aperture ratio of a display device. According to this method, a transparent planarization film is disposed as a protective film on a Thin Film Transistor (TFT) substrate, which allows a data line and a pixel electrode to overlap, thereby improving an aperture ratio compared to a conventional method. To prepare such transparent planarization films, several processing steps are employed to impart a specific pattern. High adhesion positive photoresist compositions are widely used in this process because fewer processing steps are required. Specifically, a highly adhesive positive photoresist composition containing a siloxane copolymer is known for its high heat resistance, high transparency, and low dielectric constant.

Chinese laid-open patent publication No. CN102870047A discloses a composition comprising an acrylate copolymer and a siloxane copolymer in amounts of 20 wt% or more and a photoacid compound heavy azidoquinone compound in an amount of 1 wt% to 10 wt%, and a compound containing an alcoholic hydroxyl group and/or a cyclic compound containing a carbonyl group as an organic solvent. Also disclosed is a cured film prepared from the composition, which has good heat resistance, transparency and surface hardness in addition to high dry etching resistance.

Chinese laid-open patent publication No. CN104007616A discloses a silicone photoresist composition comprising a silicone copolymer, an acrylic copolymer, a diazoquinone compound, and an organic solvent. The composition ensures the formation of a uniform planarization layer by using an alcohol ether organic solvent having a high or low boiling point in combination.

However, a planarization film prepared from a conventional high-adhesion positive photoresist composition including such a siloxane copolymer or a display device employing the same may have problems such as swelling or film-to-substrate delamination when the cured film is immersed in or contacted with an organic solvent, acid, base, or the like. That is, the adhesiveness and the film residue ratio of the photoresist composition cannot be improved to a satisfactory level.

Disclosure of Invention

In order to solve the technical problem, the invention provides a method, which comprises the following specific technical scheme:

a high-viscosity positive photoresist composition comprises an organic solvent and a solute dissolved in the organic solvent, wherein the solute comprises an epoxy group-containing siloxane copolymer, an acrylic acid copolymer, a1, 2-diazidoquinone compound and a surfactant, the weight ratio of the epoxy group-containing siloxane copolymer in the solute is 50-90wt%,

the siloxane copolymer containing the epoxy group is obtained by copolymerization of at least two silanes, the molecular formula of the silane is (R1) m (R2) n Si (OR3)4-m-n, wherein m is an integer from 0 to 3, R1 is an organic group containing the epoxy group, n is an integer from 0 to 3, R2 is any one of C1-12 alkyl, C2-10 alkenyl OR C6-15 aryl, and R3 is any one of hydrogen, C1-6 alkyl, C2-6 acyl OR C6-15 aryl.

Further, the siloxane copolymer includes a condensate of a silane compound and/or a hydrolysate thereof, the silane compound or the hydrolysate thereof being a monofunctional, bifunctional, trifunctional, or tetrafunctional silane compound, the siloxane copolymer including one or more of siloxane structural units of Q-type, T-type, D-type, or M-type.

Further, the Q-type siloxane structural unit, which comprises one silicon atom and adjacent four oxygen atoms, is derived from a hydrolysis product of a tetrafunctional silane compound or a silane compound having four hydrolyzable groups;

the T-type siloxane structural unit, which comprises one silicon atom and three adjacent oxygen atoms, is derived from a product of hydrolysis of a trifunctional silane compound or a silane compound having three hydrolyzable groups;

the D-type siloxane structural unit, which comprises one silicon atom and two adjacent oxygen atoms, is derived from a hydrolysis product of a bifunctional silane compound or a silane compound having two hydrolyzable groups;

the M-type siloxane structural unit, which includes one silicon atom and adjacent one oxygen atom, is derived from a hydrolysis product of a monofunctional silane compound or a silane compound having one hydrolyzable group.

Further, the monomers for polymerization of the acrylic copolymer include one or more of unsaturated monocarboxylic acids including (meth) acrylic acid, crotonic acid and α -chloroacrylic acid and cinnamic acid, unsaturated dicarboxylic acids and anhydrides thereof including maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid.

Further, the monomer for polymerization of the acrylic copolymer includes an ethylenically unsaturated compound having an aromatic ring, and the ethylenically unsaturated compound having an aromatic ring includes phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tribromophenyl (meth) acrylate, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, divinylbenzene, and vinylphenol.

Further, the organic solvent includes diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate and methyl 2-methoxypropionate,

the surfactant is one of a fluorine surfactant, a silicon surfactant and a nonionic surfactant.

Further, the 1, 2-diazidoquinone compound includes one or more of an ester of a phenol compound with 1, 2-diazidoquinone-4-sulfonic acid or 1, 2-diazidoquinone-5-sulfonic acid, an ester of a phenol compound with 1, 2-diazidonaphthoquinone-4-sulfonic acid or 1, 2-diazidonaphthoquinone-5-sulfonic acid, a sulfonamide of a phenol compound with a hydroxyl group substituted with an amino group with 1, 2-diazidoquinone-4-sulfonic acid or 1, 2-diazidoquinone-5-sulfonic acid, or a sulfonamide of a phenol compound with a hydroxyl group substituted with an amino group with 1, 2-diazidonaphthoquinone-4-sulfonic acid or 1, 2-diazidonaphthoquinone-5-sulfonic acid.

A method for synthesizing the high-adhesion positive photoresist composition, comprising the steps of: the method comprises the following steps:

step 1: hydrolysis reaction of silane compound: adding at least two silane compounds of the formula (R1) m (R2) n Si (OR3)4-m-n into a reaction vessel, mixing with water, the silicon-oxygen bond of the silane compounds being broken, and the silicon atom being combined with the hydroxyl group of the water atom to form silanol;

step 2: further silanol breaks a silicon-oxygen bond or breaks a hydrogen-oxygen bond;

and step 3: and (3) silane compound polycondensation reaction: the silanol with broken silicon-oxygen bonds and the silanol with broken hydrogen-oxygen bonds are continuously dehydrated and combined to form siloxane polymer;

and 4, step 4: adding a polymerization monomer and an organic solvent into another reaction container and uniformly mixing, wherein the polymerization monomer is an acrylic acid derivative;

and 5: chain initiation process: adding a free radical initiator into the reaction container, wherein the free radical initiator attacks carbon-carbon double bonds of the polymerization monomers, the carbon-carbon double bonds are broken to generate free radicals, active reaction center free radicals are formed, and the free radicals further attack the carbon-carbon double bonds of the polymerization monomers to form more active reaction center free radicals;

step 6: and (3) chain growth process: the active reaction center free radical repeatedly reacts with the carbon-carbon double bond of the acrylic acid derivative to form a macromolecular free radical;

and 7: chain termination process: the free radicals are combined and eliminated pairwise, and the free radicals are combined with each other to form stable acrylic acid copolymer;

and 8: the siloxane copolymer, the acrylic copolymer and the 1, 2-diazidoquinone compound are weighed, dissolved and mixed in an organic solvent, and the solution of the high-viscosity positive photoresist composition with the target solute content is obtained through filtration.

Further, the exacerbation reaction is carried out at 65-75 ℃, the polycondensation reaction is carried out for 7 hours under the condition of stirring at the temperature of below 20 ℃, and the reaction is accelerated by heating and refluxing.

A cured film characterized by: the cured film is made of the high-adhesion positive photoresist composition.

Further, the process for preparing the cured film is as follows: coating the photoresist composition on a substrate, prebaking to remove the organic solvent, exposing with a photomask, developing with a developer, baking and curing.

The invention has the beneficial effects that: the high-adhesion positive photoresist composition comprises a siloxane copolymer and an acrylic copolymer, wherein the siloxane copolymer and the acrylic copolymer are jointly used as an adhesive when a cured film is synthesized, the siloxane copolymer is obtained by copolymerization of at least two silanes represented by (R1) m (R2) n Si (OR3)4-m-n, the adhesion and the residual film rate of the photoresist composition are improved, and meanwhile, when the cured film prepared from the photoresist composition is immersed in an organic solvent, acid OR alkali OR is contacted with the organic solvent, acid OR alkali, the problem of swelling OR delamination of the film and a substrate is effectively solved.

Drawings

FIG. 1 is a flow chart of the preparation of a cured film of the present invention,

FIG. 2 is a schematic cross-sectional view of a process for preparing a cured film according to the present invention.

Detailed Description

The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic views illustrating only the basic structure of the present invention in a schematic manner, and thus show only the constitution related to the present invention.

As shown in FIG. 1, the high-adhesion positive photoresist composition of the present invention comprises an organic solvent and a solute dissolved in the organic solvent, wherein the solute comprises an epoxy group-containing siloxane copolymer, an acrylic acid copolymer, a1, 2-diazidoquinone compound and a surfactant, the weight ratio of the epoxy group-containing siloxane copolymer in the solute is 50-90wt%,

the siloxane copolymer containing the epoxy group is obtained by copolymerization of at least two silanes, the molecular formula of the silane is (R1) m (R2) n Si (OR3)4-m-n, wherein m is an integer from 0 to 3, R1 is an organic group containing the epoxy group, n is an integer from 0 to 3, R2 is any one of C1-12 alkyl, C2-10 alkenyl OR C6-15 aryl, and R3 is any one of hydrogen, C1-6 alkyl, C2-6 acyl OR C6-15 aryl.

The siloxane copolymer (a) contains a condensate of a silane compound and/or a hydrolysate thereof. In such cases, the silane compound or the hydrolyzate thereof may be a monofunctional to tetrafunctional silane compound.

The epoxy group-containing siloxane copolymer (a) may comprise siloxane structural units selected from the following types Q, T, D and M:

siloxane structural unit of type Q: siloxane structural units comprising one silicon atom and adjacent four oxygen atoms, which may be derived from, for example, a tetrafunctional silane compound or a hydrolysate of a silane compound having four hydrolyzable groups.

T-type siloxane structural unit: siloxane structural units comprising one silicon atom and three adjacent oxygen atoms, which may be derived from, for example, a trifunctional silane compound or a hydrolysate of a silane compound having three hydrolyzable groups.

Type D siloxane structural unit: siloxane structural units comprising one silicon atom and two adjacent oxygen atoms, which may be derived from, for example, a hydrolysis product of a bifunctional silane compound or a silane compound having two hydrolyzable groups.

M-type siloxane structural unit: siloxane structural units comprising one silicon atom and one adjacent oxygen atom may be derived from, for example, hydrolysis products of monofunctional silane compounds or silane compounds having one hydrolyzable group. For example, the siloxane copolymer (a) may include a structural unit derived from a compound represented by the following formula 1.

[ formula 1] (R1) m (R2) n Si (OR3)4-m-n in the above formula 1, m is an integer of 0 to 3, R1 is an epoxy-containing organic group, n is an integer of 0 to 3, R2 are each independently C1-12 alkyl, C2-10 alkenyl, C6-15 aryl, and R3 are each independently hydrogen, C1-6 alkyl, C2-6 acyl, OR C6-15 aryl.

Specific examples of the silane compound may include, for example,

as the tetrafunctional silane compound, tetraacetoxysilane, tetramethoxysilane, and tetraethoxysilane;

as the trifunctional silane compound, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane;

as bifunctional silane compounds, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, dimethyldiethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, 3-mercaptopropyldimethoxymethylsilane and cyclohexyldimethoxymethylsilane;

and trimethylsilane and trimethylmethoxysilane as monofunctional silane compounds.

Preferred among the tetrafunctional silane compounds are tetramethoxysilane and tetraethoxysilane;

preferred among the trifunctional silane compounds are methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane and butyltrimethoxysilane;

among the bifunctional silane compounds, preferred are dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and diphenyldiphenoxysilane.

The epoxy functional siloxane is preferably gamma-glycidoxypropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

The monomer for polymerizing the acrylic copolymer is selected from at least one of the following:

unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α -chloroacrylic acid, and cinnamic acid;

unsaturated dicarboxylic acids and their anhydrides, such as maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid.

Ethylenically unsaturated compounds having an aromatic ring, such as phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tribromophenyl (meth) acrylate, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, divinylbenzene and vinylphenol. From the viewpoint of developability, the above (meth) acrylic acid is preferable.

The acrylic copolymer (A) containing siloxane groups and fluoroalkane is prepared by the following steps: a polymerization monomer is compounded, a molecular weight controlling agent, a polymerization initiator and an organic solvent are added thereto, followed by filling nitrogen gas thereto and slowly stirring the mixture for polymerization. The molecular weight controlling agent is not particularly limited and may be a thiol compound such as butyl mercaptan and lauryl mercaptan, or a-methylstyrene dimer.

The polymerization initiator is not particularly limited and includes azo compounds such as 2,2' -azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile) and 2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile); benzoyl peroxide; lauroyl peroxide; tert-butyl peroxypivalate; or 1, 1-bis (t-butylperoxy) cyclohexane, the polymerization initiator being used alone or in combination of two or more thereof.

The organic solvent may be alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, propylene glycol alkyl ether propionates, aromatic hydrocarbons, ketones and esters.

Specific examples of the organic solvent include methanol, ethanol, tetrahydrofuran, dioxane, methyl cellosolve acetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol butyl ether acetate, toluene, xylene, methyl ethyl ketone, 4-hydroxy-4-methyl-2-pentanone, cyclopentanone, cyclohexanone, 2-heptanone, and the like, Gamma-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.

Preferred are diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate and methyl 2-methoxypropionate.

The organic solvents exemplified above may be used alone or in combination of two or more thereof.

Examples of the 1, 2-diazidoquinone compound include esters of phenol compounds with 1, 2-diazidoquinone-4-sulfonic acid or 1, 2-diazidoquinone-5-sulfonic acid; esters of phenol compounds with 1, 2-diazido naphthoquinone-4-sulfonic acid or 1, 2-diazido naphthoquinone-5-sulfonic acid; sulfonamide of phenol compounds in which the hydroxyl group is substituted with an amino group with 1, 2-diazidoquinone-4-sulfonic acid or 1, 2-diazidoquinone-5-sulfonic acid; a sulfonamide of a phenol compound in which a hydroxyl group is substituted with an amino group and 1, 2-diazido naphthoquinone-4-sulfonic acid or 1, 2-diazido naphthoquinone-5-sulfonic acid.

Hereinafter, preferred embodiments will be described to aid understanding of the present invention. However, the embodiments are shown as exemplary embodiments, and the scope of the present invention is not limited to the following embodiments.

Synthesis example 1: synthesis of epoxy group-containing siloxane copolymer A1

A reactor equipped with a reflux condenser was charged with 40 wt% of phenyltrimethoxysilane, 15 wt% of methyltrimethoxysilane, 20 wt% of 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 20 wt% of pure water. To this was added 5% by weight of propylene glycol monomethyl ether acetate, and then the mixture was stirred under reflux in the presence of 0.1% by weight of trifluoromethanesulfonic acid catalyst based on the total weight of the mixture for 7 hours, and then allowed to cool. Thereafter, the resultant product was diluted with propylene glycol methyl ether acetate so that the solid content was 40 wt%. An epoxy group containing siloxane copolymer having a weight average molecular weight of about 5,000 to 8,000 Da.

Synthesis example 2: synthesis of epoxy group-containing siloxane copolymer A2

A reactor equipped with a reflux condenser was charged with 40 wt% of phenyltrimethoxysilane, 15 wt% of methyltrimethoxysilane, 20 wt% of gamma-glycidoxypropyltrimethoxysilane and 20 wt% of pure water. To this was added 5% by weight of propylene glycol monomethyl ether acetate, and then the mixture was stirred under reflux in the presence of 0.1% by weight of trifluoromethanesulfonic acid catalyst based on the total weight of the mixture for 7 hours, and then allowed to cool. Thereafter, the resultant product was diluted with propylene glycol methyl ether acetate so that the solid content was 40 wt%. An epoxy group-containing siloxane copolymer having a weight average molecular weight of about 5,000 to 8,000Da is obtained.

Synthesis example 3: synthesis of an epoxy-free siloxane copolymer A3

A reactor equipped with a reflux condenser was charged with 50% by weight of phenyltrimethoxysilane, 25% by weight of methyltrimethoxysilane and 20% by weight of pure water, 5% by weight of propylene glycol monomethyl ether acetate was added thereto, and then the mixture was refluxed and stirred for 7 hours in the presence of 0.1% by weight of trifluoromethanesulfonic acid catalyst based on the total weight of the mixture, and then it was cooled, and the resulting product was diluted with propylene glycol methyl ether acetate so that the solid content was 40% by weight, to obtain a silicone copolymer having a synthetic weight average molecular weight of about 5,000 to 8,000Da and containing no epoxy group.

Synthesis example 4: synthesis of acrylic copolymer B

A flask equipped with a cooling tube and a stirrer was charged with 200 parts by weight of propylene glycol methyl ether acetate as a solvent, and the temperature of the solvent was raised to 70 ℃, while slowly stirring the solvent. Next, 50 parts by weight of styrene, 30 parts by weight of methyl methacrylate and 15 parts by weight of methacrylic acid were added thereto, followed by dropwise addition of 5 parts by weight of 2,2' -azobis (2, 4-dimethylvaleronitrile) as a radical polymerization initiator over 6 hours to carry out polymerization. Then, the resulting product was diluted with propylene glycol methyl ether acetate so that the solid content was 32% by weight, to obtain an acrylic copolymer having a weight average molecular weight of about 9,000 to 11,000 Da.

The components used in the examples and comparative examples are specified in the following table:

example 1:

7g of siloxane copolymer A1 of Synthesis example 1, 15g of the acrylic copolymer of Synthesis example 4, 1g of 1, 2-diazidoquinone compound and 0.02g of a surfactant were uniformly mixed. In such cases, the respective contents are those based on the solid content excluding the solvent. The mixture was dissolved in propylene glycol methyl ether acetate so that the solid content of the mixture was 25 wt%. The solution was stirred for 2 hours and filtered through a membrane filter having a pore size of 0.1 μm to obtain a composition solution having a solid content of 25 wt%.

Example 2 and comparative example 3:

the difference from example 1 is in the kind and content of components used for synthesizing the acrylic copolymer.

The following table specifically shows:

test example 1: evaluation of residual film rate

The resin compositions prepared in examples and comparative examples were each coated on a glass substrate by spin coating. The coated substrate was then pre-baked on a hot plate held at 100 ℃ for 90 seconds to form a dried film. The dried film was developed with a developer (which is a 2.5 wt% aqueous solution of TMAH) at 23 ℃ for 60 seconds. Then, an aligner (model name: MA6) emitting light having a wavelength of 200nm to 450nm was used, based on the wavelength of 365nm, at 200mJ/cm²Is such that it is exposed for a certain period of time. Thereafter, the thus-obtained exposed film was heated in a convection oven at 230 ℃ for 30 minutes to prepare a cured film having a thickness of 2 μm. The residual film ratio (%) was obtained by calculating the percentage ratio of the film thickness after post-baking to the film thickness after pre-baking obtained using a measuring instrument (SNU Precision) from the following equation 1, and the higher the value, the better the residual film effect. Specifically, if the residual film ratio is 50% or more, it is evaluated as good, and if it is 70% or more, it is evaluated as excellent.

Residual film ratio (%) (film thickness after post-baking/film thickness after pre-baking) × 100

Test example 2: evaluation of tackiness

The copolymer compositions prepared in examples and comparative examples were each coated onto a glass substrate by spin coating. The coated substrate was then pre-baked on a hot plate held at 100 ℃ for 90 seconds to form a dried film. A cured film was obtained in the same manner as in example 1 except that a photomask in which each pattern of 6 lines in the range of 1 μm to 30 μm was separated at 1 μm intervals was applied. Then, the degree of the pattern of the minimum line remaining in the 1 to 30 μm line pattern on the silicon nitride substrate was observed using a microscope. During microscopic observation, the lowest CD-sized pattern remaining after the line pattern was separated from the mask was evaluated as development adhesion. The smaller the minimum residual pattern size, the better the development adhesion. Specifically, if the minimum residual pattern size is 4 μm or less, the mark is excellent. If it is 5 μm to less than 8 μm, the label is normal. If it is 8 μm or more, it is marked as a failure.

The key performance comparison results are given in the following table:

recipe number	Residual film ratio (%)	Tackiness (pattern size μm)	Tackiness (grade judgment)
				Example 1	76.3	3μm	Is excellent in
Example 2	75.8	3μm	Is excellent in
				Comparative example 1	49.2	9μm	Fail to be qualified

As shown in the above table, the compositions of the examples within the scope of the present invention are generally excellent in terms of tackiness and film residue ratio; in contrast, the compositions of the comparative examples that are not within the scope of the present invention show at least one of these properties to be disadvantageous.

In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.