CN114437359B - Photosensitive resin composition for transparent photoresist - Google Patents
Photosensitive resin composition for transparent photoresist Download PDFInfo
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- CN114437359B CN114437359B CN202210232002.8A CN202210232002A CN114437359B CN 114437359 B CN114437359 B CN 114437359B CN 202210232002 A CN202210232002 A CN 202210232002A CN 114437359 B CN114437359 B CN 114437359B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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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
Abstract
The invention belongs to the technical field of photoresist, and discloses a photosensitive resin composition for transparent photoresist, which is prepared by the steps of firstly carrying out free radical polymerization on ethylenically unsaturated carboxylic acid and acrylate comonomer to obtain a main chain prepolymer containing carboxyl, then carrying out free radical polymerization on glycidyl methacrylate and caprolactone acrylate to obtain a side chain prepolymer containing epoxy and hydroxyethyl, grafting the side chain prepolymer on the main chain prepolymer to obtain an intermediate, and finally reacting the intermediate with ethylenically unsaturated anhydride. The photosensitive resin composition for the transparent photoresist, which has flexibility and hardness, is obtained by specially designing the structures of the main chain and the side chain and synthesizing, and the transparent photoresist prepared by using the photosensitive resin composition for the transparent photoresist as film-forming resin has the characteristics of excellent adhesive force, high transmittance, good resolution, good yellowing resistance and the like.
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to a photosensitive resin composition for transparent photoresist.
Background
The photoresist, also called as photoresist, is an important raw material for industries such as semiconductors, flat panel displays, PCBs and the like, and plays a key role in driving the upgrading and performance improvement of products in the technical upgrading process. The transparent photoresist is one of photoresists, is widely applied to the field of touch screens, is a key material of flat panel displays, and generally comprises main components such as photosensitive resin, a sensitizer, a solvent and the like. Since the photosensitive resin has an important influence on the performance of the transparent photoresist as a film-forming resin, research on the photosensitive resin has been a focus of research. The transparent photoresist is applied to the interior of the touch screen, so the transparent photoresist has the performance requirements of transparency, no yellowing, good adhesive force and the like.
The currently commonly used photoresist film-forming resins mainly include phenolic resins, poly-p-hydroxystyrene and derivatives thereof, polyester cyclic acrylate and copolymers thereof, polymethyl methacrylate, polymethacrylate glycidyl ester and the like. The polymethacrylate glycidyl ester and the copolymer thereof have high sensitivity and are easy to polymerize, so that the research is focused, but the methacrylate glycidyl ester in the methacrylate glycidyl ester and the copolymer thereof is positioned in a main chain at present, the resolution of the photoresist prepared from the methacrylate glycidyl ester is not high, and an adhesion promoter is required to be additionally added to improve the adhesion of the photoresist.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the present invention is directed to a photosensitive resin composition for a transparent photoresist.
The technical scheme of the invention is as follows:
a photosensitive resin composition for a transparent photoresist is prepared by the steps of carrying out free radical polymerization on ethylenically unsaturated carboxylic acid and acrylate comonomer to obtain a first prepolymer containing carboxyl, carrying out free radical polymerization on glycidyl methacrylate and caprolactone acrylate to obtain a second prepolymer containing epoxy and hydroxyethyl, grafting the second prepolymer on the first prepolymer to obtain an intermediate, and finally reacting the intermediate with ethylenically unsaturated acid anhydride.
Preferably, the acrylate comonomer comprises a first acrylate monomer selected from one or more of methyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth) acrylate, a second acrylate monomer selected from one or more of isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyloxy) ethyl (meth) acrylate; the third acrylate monomer is diether fluorene acrylate.
Preferably, the molar ratio of the carboxyl-containing acrylate monomer to the first acrylate monomer to the second acrylate monomer to the third acrylate monomer is (5 to 8): (4 to 8): (2 to 5): (2 to 5).
Preferably, the molar ratio between the glycidyl methacrylate and the caprolactone acrylate is (1 to 1.5): 1.
preferably, the molar ratio of the carboxyl groups in the first prepolymer to the epoxy groups in the second prepolymer is (1 to 1.05): 1.
preferably, the molar ratio between the hydroxyl groups and the unsaturated anhydride in the intermediate is 1: (1 to 1.05).
A method for preparing the photosensitive resin composition for the transparent photoresist comprises the following steps:
s1, uniformly mixing ethylenically unsaturated carboxylic acid, an acrylate comonomer, a molecular weight regulator I and a solvent I to obtain a reaction liquid I, uniformly mixing an initiator I and the solvent I to obtain an initiator solution I, adding 1/4 to 1/5 of the reaction liquid I into a reaction kettle provided with a stirrer, a condensation pipe and a thermometer, starting stirring, heating to 60 to 65 ℃, adding 1/2 to 2/3 of the initiator solution I, dropwise adding the rest of the reaction liquid I and the initiator solution I into the reaction kettle, finishing dropwise adding within 2 to 3 hours, and preserving heat for 3 to 3.5 hours to obtain a first prepolymer;
s2, obtaining a reaction solution II by using glycidyl methacrylate, caprolactone acrylate, a molecular weight regulator II and a solvent II, dissolving an initiator II in the solvent II to obtain an initiator solution II, putting 1/4 to 1/5 of the reaction solution II into a reaction kettle with a stirrer, a reflux condenser tube and a thermometer, starting stirring, heating to 60 to 65 ℃, adding 1/2 to 2/3 of the initiator solution II, dropwise adding the rest of the reaction solution II and the initiator solution II into the reaction kettle, dropwise adding the rest of the reaction solution II and the initiator solution II within 3 to 3.5 hours, and after dropwise adding, keeping the temperature for 2.5 to 3 hours to obtain a second prepolymer;
s3, adding the first prepolymer, the second prepolymer and the catalyst I into a reaction kettle provided with a stirrer, a reflux dehydration device and a thermometer, starting stirring, heating to 100-110 ℃, carrying out reflux reaction, detecting the acid value of the system at intervals, and stopping the reaction when the acid value is not changed any more to obtain an intermediate;
s4, adding the ethylenically unsaturated anhydride into the intermediate in a dropwise manner, adding a catalyst II and a polymerization inhibitor, starting stirring, heating to 85-90 ℃, detecting the acid value of the system at intervals, and stopping reaction when the acid value is not changed any more to obtain the photosensitive resin composition for the transparent photoresist.
Preferably, the addition amount of the molecular weight regulator I is 0.5-0.7% of the mass of the reaction liquid I, and the addition amount of the initiator I is 0.7-1% of the mass of the reaction liquid I; in the step S2, the addition amount of the molecular weight regulator II is 2-2.5% of the mass of the reaction liquid II, and the addition amount of the initiator II is 0.7-1% of the mass of the reaction liquid II.
Preferably, the addition amount of the catalyst I is 1-2% of the mass of the first prepolymer; in the step S4, the addition amount of the catalyst II is 1-2% of the mass of the intermediate, and the addition amount of the polymerization inhibitor is 4-8% of the mass of the reaction system.
Compared with the prior art, the invention has the beneficial effects that:
the photosensitive resin composition for the transparent photoresist, which has flexibility and hardness, is obtained by specially designing the structures of the main chain and the side chain and synthesizing, and the transparent photoresist prepared by using the photosensitive resin composition for the transparent photoresist as a film-forming resin has the characteristics of excellent adhesive force, high transmittance, good resolution, good yellowing resistance and the like.
Detailed Description
The present invention is described more fully below in order to provide a better understanding of the present invention by those skilled in the art.
A photosensitive resin composition for a transparent photoresist is prepared by the steps of carrying out free radical polymerization on ethylenically unsaturated carboxylic acid and acrylate comonomer to obtain a first prepolymer containing carboxyl, carrying out free radical polymerization on glycidyl methacrylate and caprolactone acrylate to obtain a second prepolymer containing epoxy and hydroxyethyl, grafting the second prepolymer onto the first prepolymer to obtain an intermediate, and finally reacting the intermediate with ethylenically unsaturated anhydride.
The acrylate comonomer comprises a first acrylate monomer, a second acrylate monomer and a third acrylate monomer, wherein the first acrylate monomer is selected from one or more of methyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate and tert-butyl (meth) acrylate, and the second acrylate monomer is selected from one or more of isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate and dicyclopentadienyloxy ethyl (meth) acrylate; the third acrylate monomer is diether fluorene acrylate.
Wherein the ethylenically unsaturated carboxylic acid is selected from methacrylic acid or acrylic acid.
Wherein the ethylenically unsaturated anhydride is maleic anhydride.
Wherein the molar ratio of the carboxyl-containing acrylate monomer to the first acrylate monomer to the second acrylate monomer to the third acrylate monomer is (5 to 8): (4 to 8): (2 to 5): (2 to 5).
Wherein the molar ratio of the glycidyl methacrylate to the caprolactone acrylate is (1 to 1.5): 1.
wherein the molar ratio of the carboxyl in the first prepolymer to the epoxy in the second prepolymer is (1 to 1.05): 1.
wherein the molar ratio between the hydroxyl groups and the unsaturated acid anhydride in the intermediate is 1: (1 to 1.05).
A method for preparing the photosensitive resin composition for the transparent photoresist comprises the following steps:
s1, uniformly mixing ethylenically unsaturated carboxylic acid, an acrylate comonomer, a molecular weight regulator I and a solvent I to obtain a reaction liquid I, uniformly mixing an initiator I and the solvent I to obtain an initiator solution I, adding 1/4 to 1/5 of the reaction liquid I into a reaction kettle with a stirrer, a condensation pipe and a thermometer, starting stirring, heating to 60 to 65 ℃, adding 1/2 to 2/3 of the initiator solution reaction liquid I, dropwise adding the rest of the reaction liquid I and the initiator solution I into the reaction kettle, dropwise adding the rest of the reaction liquid I and the initiator solution I within 2 to 3 hours, and after dropwise adding, keeping the temperature for 3 to 3.5hours to obtain a first prepolymer;
s2, obtaining a reaction liquid II by using glycidyl methacrylate, caprolactone acrylate, a molecular weight regulator II and a solvent II, dissolving an initiator II in the solvent II to obtain an initiator solution II, putting 1/4 to 1/5 of the reaction liquid II into a reaction kettle provided with a stirrer, a reflux condenser tube and a thermometer, starting stirring, heating to 60 to 65 ℃, adding 1/2 to 2/3 of the initiator solution II, dropwise adding the rest of the reaction liquid II and the initiator solution II into the reaction kettle, completing dropwise adding within 3 to 3.5 hours, and after completing dropwise adding, keeping the temperature for 2.5 to 3 hours to obtain a second prepolymer;
s3, adding the first prepolymer, the second prepolymer and the catalyst I into a reaction kettle provided with a stirrer, a reflux dehydration device and a thermometer, starting stirring, heating to 100-110 ℃, carrying out reflux reaction, detecting the acid value of the system at intervals, and stopping the reaction when the acid value is not changed any more to obtain an intermediate;
s4, adding the ethylenically unsaturated anhydride into the intermediate in a dropwise manner, adding a catalyst II and a polymerization inhibitor, stirring, heating to 85-90 ℃, detecting the acid value of the system at intervals, and stopping reaction when the acid value is not changed any more to obtain the photosensitive resin composition for the transparent photoresist.
Wherein, the initiator I and the initiator II can be selected from one of tert-butyl peroxy-2-ethylhexanoate, 1-bis (tert-amyl peroxy) cyclohexane, tert-amyl peroxyacetate, azobisisobutyronitrile and azobisisoheptonitrile.
Wherein, the molecular weight regulator I and the molecular weight regulator II can be one or more selected from n-dodecyl mercaptan, tert-dodecyl mercaptan and AMSD. AMSD may be preferred from the viewpoint of odor.
Among them, catalyst I is triphenylphosphine, because epoxy group has higher activity than hydroxyl group, carboxyl group and epoxy group have nucleophilic substitution reaction preferentially, therefore triphenylphosphine is selected to make reaction proceed more easily.
Wherein the catalyst II is p-toluenesulfonic acid.
Wherein the polymerization inhibitor is one or more of p-hydroxyanisole, 2-tert-butylhydroquinone or hydroquinone.
Wherein the solvent I and the solvent II are mixed solvents consisting of n-butyl alcohol and ethylene glycol ethyl ether, and the volume ratio of the n-butyl alcohol to the ethylene glycol ethyl ether is 1.
Wherein the addition amount of the molecular weight regulator I is 0.5-0.7% of the mass of the reaction liquid I, and the addition amount of the initiator I is 0.7-1% of the mass of the reaction liquid I; in the step S2, the addition amount of the molecular weight regulator II is 2-2.5% of the mass of the reaction liquid II, and the addition amount of the initiator II is 0.7-1% of the mass of the reaction liquid II.
Wherein the addition amount of the catalyst I is 1-2% of the mass of the first prepolymer; in the step S4, the addition amount of the catalyst II is 1-2% of the intermediate, and the addition amount of the polymerization inhibitor is 4-8% of the mass of the reaction system.
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated. In the present specification, "part" and "%" represent "part by mass" and "% by mass", respectively, unless otherwise specified.
Example 1
A method for preparing the photosensitive resin composition for the transparent photoresist comprises the following steps:
s1, uniformly mixing acrylic acid, methyl methacrylate, isobornyl acrylate, diether fluorene acrylate, a molecular weight regulator AMSD and a mixed solvent (n-butyl alcohol and ethylene glycol ethyl ether mixed according to a volume ratio of 1; wherein the feeding molar ratio of methacrylic acid, methyl methacrylate, isobornyl acrylate and diether fluorene acrylate is 5:8:2:5, the addition amount of the molecular weight regulator I is 0.5 percent of the mass of the reaction liquid I, and the addition amount of the tert-butyl peroxy-2-ethylhexanoate is 0.7 percent;
s2, preparing a reaction solution II by mixing glycidyl methacrylate, caprolactone acrylate (TONE M-201), a molecular weight regulator AMSD and a mixed solvent (n-butyl alcohol and ethylene glycol ethyl ether mixed according to a volume ratio of 1; wherein the molar ratio of the glycidyl methacrylate to the caprolactone acrylate is 1.5:1, the addition amount of the molecular weight adjusting AMSD is 2% of the mass of the reaction liquid II, and the addition amount of the tert-butyl peroxy-2-ethylhexanoate is 0.7% of the mass of the reaction liquid II;
s3, adding the first prepolymer, the second prepolymer and triphenylphosphine into a reaction kettle provided with a stirrer, a reflux dehydration device and a thermometer, starting stirring, heating to 100 ℃, carrying out reflux reaction, detecting the acid value of the system at intervals, and stopping the reaction when the acid value is not changed any more to obtain an intermediate; wherein the molar ratio of the carboxyl groups in the first prepolymer to the epoxy groups in the second prepolymer is 1:1, adding triphenylphosphine in an amount of 2% of the mass of the first prepolymer;
s4, adding maleic anhydride into the intermediate in a dropwise manner, adding p-toluenesulfonic acid and p-hydroxyanisole, starting stirring, heating to 90 ℃, detecting the acid value of the system at intervals, stopping the reaction when the acid value is not changed any more, and obtaining the photosensitive resin composition for the transparent photoresist, wherein the molar ratio of hydroxyl in the intermediate to unsaturated anhydride is 1:1, the addition amount of the p-toluenesulfonic acid is 2% of that of the intermediate, and the addition amount of the polymerization inhibitor is 8 per mill of the mass of the reaction system.
Example 2
A method for preparing the photosensitive resin composition for the transparent photoresist comprises the following steps:
s1, uniformly mixing methacrylic acid, methyl tert-butyl acrylate, isobornyl acrylate, diether fluorene acrylate, a molecular weight regulator AMSD and a mixed solvent (n-butyl alcohol and ethylene glycol ethyl ether mixed according to a volume ratio of 1; wherein the feeding molar ratio of methacrylic acid, methyl tert-butyl acrylate, isobornyl acrylate and diether fluorene acrylate is 8:4:5:2, the addition amount of the molecular weight regulator I is 0.5 percent of the mass of the reaction liquid I, and the addition amount of the tert-butyl peroxy-2-ethylhexanoate is 0.7 percent;
s2, preparing a reaction solution II from glycidyl methacrylate, caprolactone acrylate (TONE M-201), a molecular weight regulator AMSD and a mixed solvent (n-butyl alcohol and ethylene glycol ether mixed in a volume ratio of 1; wherein the molar ratio of the glycidyl methacrylate to the caprolactone acrylate is 1:1, the addition amount of the molecular weight adjusting AMSD is 2.5 percent of the mass of the reaction liquid II, and the addition amount of the tert-butyl peroxy-2-ethylhexanoate is 1 percent of the mass of the reaction liquid II;
s3, adding the first prepolymer, the second prepolymer and triphenylphosphine into a reaction kettle provided with a stirrer, a reflux dehydration device and a thermometer, starting stirring, heating to 100 ℃, carrying out reflux reaction, detecting the acid value of the system at intervals, and stopping the reaction when the acid value is not changed any more to obtain an intermediate; wherein the molar ratio of the carboxyl in the first prepolymer to the epoxy in the second prepolymer is 1.05:1, the addition amount of triphenylphosphine is 1.5 percent of the mass of the first prepolymer;
s4, adding maleic anhydride into the intermediate in a dropwise manner, adding p-toluenesulfonic acid and p-hydroxyanisole, starting stirring, heating to 90 ℃, detecting the acid value of the system at intervals, stopping the reaction when the acid value is not changed any more, and obtaining the photosensitive resin composition for the transparent photoresist, wherein the molar ratio of hydroxyl in the intermediate to unsaturated anhydride is 1:1.05, the addition amount of the p-toluenesulfonic acid is 1.5 percent of that of the intermediate, and the addition amount of the polymerization inhibitor is 8 per mill of the mass of the reaction system.
Example 3
A method for preparing the photosensitive resin composition for the transparent photoresist comprises the following steps:
s1, uniformly mixing methacrylic acid, methyl tert-butyl acrylate, cyclohexyl acrylate, diether fluorene acrylate, a molecular weight regulator AMSD and a mixed solvent (n-butyl alcohol and ethylene glycol ethyl ether mixed in a volume ratio of 1; wherein the feeding molar ratio of methacrylic acid, methyl tert-butyl acrylate, isobornyl acrylate and diether fluorene acrylate is 7:5:5:2, the addition amount of the molecular weight regulator I is 0.5 percent of the mass of the reaction liquid I, and the addition amount of the tert-butyl peroxy-2-ethylhexanoate is 0.7 percent;
s2, preparing a reaction solution II from glycidyl methacrylate, caprolactone acrylate (TONE M-201), a molecular weight regulator AMSD and a mixed solvent (n-butyl alcohol and ethylene glycol ether mixed in a volume ratio of 1; wherein the molar ratio of the glycidyl methacrylate to the caprolactone acrylate is 1:1, the addition amount of the molecular weight adjusting AMSD is 2.5 percent of the mass of the reaction liquid II, and the addition amount of the tert-butyl peroxy-2-ethylhexanoate is 1 percent of the mass of the reaction liquid II;
s3, adding the first prepolymer, the second prepolymer and triphenylphosphine into a reaction kettle provided with a stirrer, a reflux dehydration device and a thermometer, starting stirring, heating to 110 ℃, carrying out reflux reaction, detecting the acid value of the system at intervals, and stopping the reaction when the acid value is not changed any more to obtain an intermediate; wherein the molar ratio of the carboxyl groups in the first prepolymer to the epoxy groups in the second prepolymer is 1:1, the addition amount of triphenylphosphine is 1 percent of the mass of the first prepolymer;
s4, adding maleic anhydride into the intermediate in a dropwise manner, adding p-toluenesulfonic acid and p-hydroxyanisole, starting stirring, heating to 90 ℃, detecting the acid value of the system at intervals, stopping the reaction when the acid value is not changed any more, and obtaining the photosensitive resin composition for the transparent photoresist, wherein the molar ratio of hydroxyl in the intermediate to unsaturated anhydride is 1:1, the addition amount of the p-toluenesulfonic acid is 1 percent of that of the intermediate, and the addition amount of the polymerization inhibitor is 4 per mill of the mass of the reaction system.
Example 4
The photosensitive resin compositions for transparent resists prepared in examples 1 to 3 were each subjected to a performance test.
The method for preparing the transparent photoresist comprises the following steps:
25 parts of the photosensitive resin composition for a clear resist prepared in examples 1 to 3 were uniformly mixed with 1 part of a photoinitiator 907, 1 part of a photoinitiator ITX, 5 parts of tripropylene glycol diacrylate, 5 parts of trimethylolpropane triacrylate, 20 parts of propylene glycol methyl ether acetate, 20 parts of cyclohexanone, 10 parts of ethyl acetate, and 0.05 part of a leveling agent (EFKA 3883 of Pasff), respectively, to obtain clear resists A1 to A3.
The test panels were prepared as follows:
respectively spin-coating transparent photoresists A1-A3 on a clean ITO glass substrate, controlling the spin-coating thickness to be 2 microns, baking for 90 seconds at 90 ℃, performing mask exposure treatment, soaking for 90 seconds by using 0.05% KOH solution for development, putting the developed substrate into an oven, baking for 30 minutes at 130 ℃ to obtain a test sample plate, and respectively performing adhesion, light transmittance, resolution, yellowing resistance and hardness tests on the test sample plate, wherein the test results are shown in Table 1.
The test method is as follows:
adhesion force: and scribing a louver on one surface of the test sample plate coated with the transparent photoresist by using a knife, attaching a 3M adhesive tape to the center position of the louver, quickly and continuously pulling away, judging whether the coating is completely free of falling off as 5B, the falling off degree is less than 5% as 4B, the falling off degree is 5-15% as 3B, the falling off degree is 15-35% as 2B, the falling off degree is 35-65% as 1B, and the falling off degree is more than 65% as 0B according to the falling off condition of the coating.
Boiling resistance: and (3) placing the test sample plate in boiling water, boiling for 1 hour, and then carrying out adhesion test.
Light transmittance: and (3) measuring the light transmittance of the test sample plate at the wavelength of 400nm by using an ultraviolet-visible spectrophotometer, wherein the light transmittance is larger than 98 percent, and the mark is qualified.
Resolution ratio: on the test sample plate, the state after development of 20 μm pores was observed: this resolution is considered to be achieved if the development is clean and the diameter of the pores is in the range of 20 ± 2 μm; if the development is clean, but the pore diameter is not in the range of 20. + -.2 μm, it is considered that the resolution cannot be achieved; if the 20 μm holes are not developed cleanly, the resolution is considered to be not achieved. By analogy, if 20 μm wells are not as desired, 30 μm, 40 μm, 50 μm wells are observed until a clean development is found and the size variation is within plus or minus 10% of the Mask size.
Anti-yellowing: the above test panel was baked at 230 ℃ for 30min and then tested for transmittance at 400nm, and yellowing resistance was expressed as the percentage of transmittance measured after baking and transmittance measured before baking.
TABLE 1
As can be seen from Table 1, the transparent photoresists prepared from the photosensitive resins obtained in examples 1 to 3 of the present invention as film-forming resins have excellent adhesion, high light transmittance, yellowing resistance, high resolution, and the like. According to the invention, through specially designing the structure of the molecular chain, the obtained photosensitive resin can be applied to the transparent photoresist, an adhesion promoter is not required to be additionally added, and the prepared transparent photoresist has excellent adhesion and boiling resistance.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (5)
1. The photosensitive resin composition for the transparent photoresist is characterized by being prepared by the steps of firstly, carrying out free radical polymerization on ethylenically unsaturated carboxylic acid and acrylate comonomer to obtain a first prepolymer containing carboxyl, then carrying out free radical polymerization on glycidyl methacrylate and caprolactone acrylate to obtain a second prepolymer containing epoxy and hydroxyethyl, grafting the second prepolymer onto the first prepolymer to obtain an intermediate, and finally reacting the intermediate with ethylenically unsaturated anhydride;
the acrylate comonomer comprises a first acrylate monomer, a second acrylate monomer and a third acrylate monomer, wherein the first acrylate monomer is selected from one or more of methyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate and tert-butyl (meth) acrylate, and the second acrylate monomer is selected from one or more of isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate and dicyclopentadienyloxy ethyl (meth) acrylate; the third acrylate monomer is diether fluorene acrylate;
the molar ratio of the glycidyl methacrylate to the caprolactone acrylate is (1 to 1.5): 1;
the molar ratio of carboxyl groups in the first prepolymer to epoxy groups in the second prepolymer is (1 to 1.05): 1;
the molar ratio between the hydroxyl groups and the unsaturated acid anhydride in the intermediate is 1: (1 to 1.05);
the ethylenically unsaturated carboxylic acid is methacrylic acid or acrylic acid.
2. The photosensitive resin composition for a transparent photoresist according to claim 1, wherein the molar ratio of the carboxyl group-containing acrylate monomer to the first acrylate monomer to the second acrylate monomer to the third acrylate monomer is (5 to 8): (4 to 8): (2 to 5): (2 to 5).
3. A method for producing the photosensitive resin composition for a transparent resist according to any one of claims 1 to 2, comprising the steps of:
s1, uniformly mixing ethylenically unsaturated carboxylic acid, an acrylate comonomer, a molecular weight regulator I and a solvent I to obtain a reaction liquid I, uniformly mixing an initiator I and the solvent I to obtain an initiator solution I, adding 1/4 to 1/5 of the reaction liquid I into a reaction kettle with a stirrer, a condensation pipe and a thermometer, starting stirring, heating to 60 to 65 ℃, adding 1/2 to 2/3 of the initiator solution reaction liquid I, dropwise adding the rest of the reaction liquid I and the initiator solution I into the reaction kettle, dropwise adding the rest of the reaction liquid I and the initiator solution I within 2 to 3 hours, and after dropwise adding, keeping the temperature for 3 to 3.5hours to obtain a first prepolymer;
s2, obtaining a reaction liquid II by using glycidyl methacrylate, caprolactone acrylate, a molecular weight regulator II and a solvent II, dissolving an initiator II in the solvent II to obtain an initiator solution II, putting 1/4 to 1/5 of the reaction liquid II into a reaction kettle provided with a stirrer, a reflux condenser tube and a thermometer, starting stirring, heating to 60 to 65 ℃, adding 1/2 to 2/3 of the initiator solution II, dropwise adding the rest of the reaction liquid II and the initiator solution II into the reaction kettle, completing dropwise adding within 3 to 3.5 hours, and after completing dropwise adding, keeping the temperature for 2.5 to 3 hours to obtain a second prepolymer;
s3, adding the first prepolymer, the second prepolymer and a catalyst I into a reaction kettle provided with a stirrer, a reflux dehydration device and a thermometer, starting stirring, heating to 100-110 ℃, carrying out reflux reaction, detecting the acid value of the system at intervals, and stopping the reaction when the acid value is not changed any more to obtain an intermediate;
s4, adding the ethylenically unsaturated anhydride into the intermediate in a dropwise manner, adding a catalyst II and a polymerization inhibitor, starting stirring, heating to 85-90 ℃, detecting the acid value of the system at intervals, and stopping reaction when the acid value is not changed any more to obtain the photosensitive resin composition for the transparent photoresist.
4. The method according to claim 3, wherein in step S1, the addition amount of the molecular weight regulator I is 0.5-0.7% of the mass of the reaction solution I, and the addition amount of the initiator I is 0.7-1% of the mass of the reaction solution I; in the step S2, the addition amount of the molecular weight regulator II is 2-2.5% of the mass of the reaction liquid II, and the addition amount of the initiator II is 0.7-1% of the mass of the reaction liquid II.
5. The process of claim 4, wherein in step S3, the amount of catalyst I added is 1% to 2% of the mass of the first prepolymer; in the step S4, the addition amount of the catalyst II is 1-2% of the mass of the intermediate, and the addition amount of the polymerization inhibitor is 4-8% of the mass of the reaction system.
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| CN106796396A (en) * | 2015-11-02 | 2017-05-31 | 互应化学工业株式会社 | Photosensitive polymer combination, dry film and printed wiring board |
| CN111285956A (en) * | 2019-12-31 | 2020-06-16 | 深圳市安立微电子材料有限公司 | Polymer resin and negative photoresist |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2862313B2 (en) * | 1990-02-28 | 1999-03-03 | 山栄化学株式会社 | Solder resist ink composition and cured product thereof |
| JP3503910B2 (en) * | 1994-08-17 | 2004-03-08 | 互応化学工業株式会社 | Photo solder resist ink, printed circuit board and method of manufacturing the same |
| JP3614152B2 (en) * | 2001-08-07 | 2005-01-26 | 株式会社村田製作所 | Photosensitive conductive paste, circuit board using the same, and method for producing ceramic multilayer substrate |
| US20040265494A1 (en) * | 2003-06-25 | 2004-12-30 | Szuping Lu | Glycidyl (meth)acrylate powder coating compositions containing caprolactone-derived side chains |
| JP6157193B2 (en) * | 2013-04-22 | 2017-07-05 | 昭和電工株式会社 | (Meth) acrylate polymer, composition containing the polymer and use thereof |
| JPWO2015040908A1 (en) * | 2013-09-20 | 2017-03-02 | 東洋紡株式会社 | Photosensitive conductive paste, conductive thin film, electric circuit, and touch panel |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10306138A (en) * | 1997-03-03 | 1998-11-17 | Hitachi Chem Co Ltd | Photosensitive resin composition and production of printed wiring board using the same |
| JP2003270786A (en) * | 2002-03-14 | 2003-09-25 | Goo Chemical Co Ltd | Photosensitive resin composition, photo-solder resist ink, printed wiring board, flexible printed wiring board and dry film |
| CN106796396A (en) * | 2015-11-02 | 2017-05-31 | 互应化学工业株式会社 | Photosensitive polymer combination, dry film and printed wiring board |
| CN111285956A (en) * | 2019-12-31 | 2020-06-16 | 深圳市安立微电子材料有限公司 | Polymer resin and negative photoresist |
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