CN112011031A - Negative photoresist resin, preparation method thereof and negative photoresist - Google Patents
Negative photoresist resin, preparation method thereof and negative photoresist Download PDFInfo
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- CN112011031A CN112011031A CN202010804728.5A CN202010804728A CN112011031A CN 112011031 A CN112011031 A CN 112011031A CN 202010804728 A CN202010804728 A CN 202010804728A CN 112011031 A CN112011031 A CN 112011031A
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Abstract
The invention discloses a negative photoresist resin, a preparation method thereof and the negative photoresist resin, which comprises the following components in parts by weight: 20 to 40 parts of monomolecular solid epoxy resin, 15 to 35 parts of acryloyl oxypolymethylene carboxylic acid, 10 to 30 parts of anhydride, 10 to 25 parts of high boiling point solvent, 0.08 to 0.2 part of polymerization inhibitor and 0.1 to 0.3 part of catalyst. The negative photoresist resin provided by the invention takes the monomolecular solid epoxy resin as the main resin, the main resin adopts monomolecular substances for reaction in the modification procedure, and the finally obtained negative photoresist resin is also monomolecular resin, so that all the negative photoresist resins are ensured to have the same photocuring sensitivity and developing speed. Moreover, the surface drying property and the developing property of the monomolecular solid epoxy resin are good, and the resolution of the negative photoresist can be obviously improved.
Description
Technical Field
The present invention relates to the field of photoresists, in particular, to a negative-type photoresist resin. In addition, the invention also relates to a preparation method of the negative photoresist resin and a negative photoresist.
Background
With the development of AI technology and the coming of the 5G era, chip technology is rapidly developing, gradually going from the micrometer level to the nanometer level, and in order to improve the resolution, the resolution of the photoresist needs to be improved first. The traditional negative photoresist adopts modified epoxy resin, polyester resin, alkyd resin, polyvinyl alcohol laurate and the like with large molecular weight as main resin, and because the molecular weight distribution of the resin mostly presents normal distribution or beta type distribution, the molecular weight of the resin in the same batch has large and small difference. The development rates based on different molecular weights vary widely, with the consequences: developing the resin with small molecular weight, wherein when the resin with small molecular weight is developed completely, the macromolecular resin is possibly developed but not yet; or after the macromolecular resin is developed cleanly, the small molecular resin can generate an over-development phenomenon, so that lines and edges after development are irregular, the resolution ratio of the negative photoresist cannot be improved, and the chip is difficult to reach a nanometer level.
Disclosure of Invention
The invention provides a negative photoresist resin, a preparation method thereof and a negative photoresist, and aims to solve the technical problem that the resolution of the negative photoresist is low due to uneven molecular weight distribution after the traditional negative photoresist adopts a high molecular weight resin as a main resin.
The technical scheme adopted by the invention is as follows:
a negative photoresist resin comprising, in parts by weight: 20 to 40 parts of monomolecular solid epoxy resin, 15 to 35 parts of acryloyl oxypolymethylene carboxylic acid, 10 to 30 parts of anhydride, 10 to 25 parts of high boiling point solvent, 0.08 to 0.2 part of polymerization inhibitor and 0.1 to 0.3 part of catalyst.
Furthermore, 24 to 40 parts of monomolecular solid epoxy resin, 18 to 34 parts of acryloyloxy polymethylene carboxylic acid, 15 to 30 parts of anhydride, 16 to 25 parts of high-boiling solvent, 0.08 to 0.2 part of polymerization inhibitor and 0.1 to 0.3 part of catalyst.
Further, the negative photoresist resin is a monomolecular resin; the epoxy value of the monomolecular solid epoxy resin is 0.3-0.95, and the monomolecular solid epoxy resin comprises at least one of triglycidyl isocyanurate, hydantoin epoxy resin, triphenol methane triglycidyl ether epoxy resin, phloroglucinol triglycidyl ether epoxy resin, triglycidyl trimesate epoxy resin, dicyclopentadiene dioxide epoxy resin, dicyclopentenyl ether dioxide epoxy resin, diglycidyl isophthalate epoxy resin and diglycidyl terephthalate epoxy resin.
Further, the acryloyloxy polymethylene carboxylic acid includes 6- (acryloyloxy) hexanoic acid or β -acryloyloxy propionic acid.
Further, the boiling point of the high-boiling-point solvent is more than or equal to 180 ℃, and the high-boiling-point solvent comprises one of dibasic ester, diethylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, ethylene glycol butyl ether acetate or propylene glycol phenyl ether acetate; and/or the acid anhydride comprises one of maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or chlorendic anhydride.
Further, the polymerization inhibitor comprises one of phenol, hydroquinone, resorcinol, p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol or phenothiazine; and/or the catalyst comprises one of triethylamine, triethanolamine, N-dimethylaniline, N-dimethylbenzylamine, triphenylphosphine, benzyltriphenylphosphonium bromide, tetrabutylphosphonium bromide, 2-mercaptobenzothiazole, diazabicyclo or lithium carbonate.
According to another aspect of the present invention, there is also provided a method of preparing the negative photoresist resin, comprising the steps of:
s1, uniformly mixing the monomolecular solid epoxy resin with the high-boiling-point solvent, and heating to fully dissolve the monomolecular solid epoxy resin to obtain a mixed solution A;
s2, adding part of polymerization inhibitor into the mixed solution A obtained in the step S1, and uniformly mixing to obtain mixed solution B;
s3, uniformly mixing the residual polymerization inhibitor, part of catalyst and acryloyl oxypolymethylene carboxylic acid to obtain a mixed solution C, slowly dropwise adding the mixed solution C into the mixed solution B obtained in the step S2, controlling the temperature to be 80-90 ℃, after dropwise adding, heating to 90-100 ℃ for reaction, and obtaining a reaction solution with the acid value of less than or equal to 0.5 mgKOH/g;
s4, adding acid anhydride and the residual catalyst into the reaction liquid obtained in the step S3, controlling the temperature to react, measuring the acid value to be less than or equal to 90mgKOH/g, and cooling to obtain the negative photoresist resin.
Further, the heating temperature of the step S1 is 80-90 ℃; the dripping time of the step S3 is 1.5 to 2.5 hours, and the reaction time is 7 to 12 hours; the temperature control temperature of the step S4 is 90-100 ℃, the reaction time is 2-3 h, and the temperature after temperature reduction is 50-60 ℃.
According to another aspect of the present invention, there is also provided a negative photoresist comprising the above negative photoresist resin.
Further, the composition comprises the following components in parts by weight: 60 to 75 portions of negative photoresist resin, 15 to 30 portions of organic solvent, 5 to 10 portions of monomer, 1 to 3 portions of photoinitiator, 0.1 to 0.5 portion of flatting agent and 0.5 to 1 portion of black dye.
The invention has the following beneficial effects:
the negative photoresist resin comprises monomolecular solid epoxy resin, acryloyloxy polymethylene carboxylic acid, acid anhydride, a high-boiling-point solvent, a polymerization inhibitor and a catalyst, wherein the monomolecular solid epoxy resin is used as a main resin, the main resin is subjected to reaction by adopting monomolecular substances in the modification process, and finally the obtained negative photoresist resin is also monomolecular resin, so that all the negative photoresist resins are ensured to have the same photocuring sensitivity and developing speed. Moreover, the surface drying property and the developing property of the monomolecular solid epoxy resin are good, and the resolution of the negative photoresist can be obviously improved. Meanwhile, the traditional acrylic acid is replaced by the acryloyloxy polymethylene carboxylic acid, the distance between a photocuring group and an alkali-soluble group of the negative photoresist resin on a molecular structure is shortened, and the photocuring sensitivity and the developing sensitivity are further improved.
The negative photoresist is prepared by using negative photoresist resin, the line edge is straight and regular after the negative photoresist is solidified and developed, the negative photoresist has high resolution, and the etched glass or silicon wafer has fine lines.
In addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention will be described in further detail below with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a flow chart of a negative photoresist resin synthesis according to a preferred embodiment 1 of the present invention; and
fig. 2 is a flow chart of a negative photoresist resin synthesis according to a preferred embodiment 3 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Fig. 1 is a flow chart of a negative photoresist resin synthesis according to a preferred embodiment 1 of the present invention; fig. 2 is a flow chart of a negative photoresist resin synthesis according to a preferred embodiment 3 of the present invention.
The negative photoresist resin of the present embodiment includes, in parts by weight: 20 to 40 parts of monomolecular solid epoxy resin, 15 to 35 parts of acryloyl oxypolymethylene carboxylic acid, 10 to 30 parts of anhydride, 10 to 25 parts of high boiling point solvent, 0.08 to 0.2 part of polymerization inhibitor and 0.1 to 0.3 part of catalyst. The negative photoresist resin comprises monomolecular solid epoxy resin, acryloyloxy polymethylene carboxylic acid, acid anhydride, a high-boiling-point solvent, a polymerization inhibitor and a catalyst, wherein the monomolecular solid epoxy resin is used as a main resin, the main resin is subjected to reaction by adopting monomolecular substances in the modification process, and finally the obtained negative photoresist resin is also monomolecular resin, so that all the negative photoresist resins are ensured to have the same photocuring sensitivity and developing speed. Moreover, the surface drying property and the developing property of the monomolecular solid epoxy resin are good, and the resolution of the negative photoresist can be obviously improved. Meanwhile, the traditional acrylic acid is replaced by the acryloyloxy polymethylene carboxylic acid, the distance between a photocuring group and an alkali-soluble group of the monomolecular negative photoresist resin on a molecular structure is increased, and the photocuring sensitivity and the developing sensitivity are further improved.
In the embodiment, the epoxy resin comprises 24 to 40 parts of monomolecular solid epoxy resin, 18 to 34 parts of acryloyloxy polymethylene carboxylic acid, 15 to 30 parts of anhydride, 16 to 25 parts of high-boiling solvent, 0.08 to 0.2 part of polymerization inhibitor and 0.1 to 0.3 part of catalyst. The negative photoresist resin prepared from the components in parts by weight is more excellent in performance.
In this embodiment, the negative photoresist resin is a monomolecular resin. The epoxy value of the monomolecular solid epoxy resin is 0.3-0.95, and the monomolecular solid epoxy resin comprises triglycidyl isocyanurate, hydantoin epoxy resin, triphenol methane triglycidyl ether epoxy resin, phloroglucinol triglycidyl ether epoxy resin, trimesic acid triglycidyl ester epoxy resin, dicyclopentadiene dioxide epoxy resin, dicyclopentenyl ether dioxide epoxy resin, isophthalic acid diglycidyl ester epoxy resin and terephthalic acid diglycidyl ester epoxy resin. The monomolecular solid epoxy resin ensures that the synthesized main resin has good surface drying performance, and avoids the phenomena of wide molecular weight distribution range of high molecular substances and inconsistent generated molecules, thereby avoiding the problems of differential photocuring sensitivity, differential developability and low resolution.
In this example, the acryloyloxy polymethylene carboxylic acid includes 6- (acryloyloxy) hexanoic acid or β -acryloyloxy propionic acid. The acryloyl oxygen polymethylene carboxylic acid is 6- (acryloyloxy) caproic acid or beta-acryloyloxy propionic acid and contains a photocuring group, wherein carboxyl of the acryloyl oxygen polymethylene carboxylic acid reacts with an epoxy group of a main resin, so that the group participating in photocuring reaction on the main resin is protruded on the outer surface of a molecular structure as much as possible, the photocuring reaction sensitivity is improved, meanwhile, the conversion rate of double bonds is obviously improved, and the etching resistance of the main resin is further improved. Moreover, the polymethylene of the acryloyloxy polymethylene carboxylic acid enables the negative photoresist resin to have better flexibility, so that the negative photoresist has excellent adhesion performance to a substrate.
In this embodiment, the high boiling point solvent has a boiling point of not less than 180 ℃, and includes one of dibasic ester, diethylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, ethylene glycol butyl ether acetate, and propylene glycol phenyl ether acetate. The high boiling point solvent can improve the leveling property of the printed negative photoresist, so that the whole thickness of the printed negative photoresist is uniform, the consistency of the light curing degree on the whole exposure surface is ensured, and the subsequent developing effect is ensured.
In this embodiment, the acid anhydride includes one of maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, or chlorendic anhydride. The maleic anhydride, the phthalic anhydride, the tetrahydrophthalic anhydride, the hexahydrophthalic anhydride or the chlorendic anhydride are anhydrides with alkali-soluble groups and of cyclic structures, and the anhydrides with cyclic structures can improve the adhesive force and the etching resistance of the formed negative photoresist and improve the developing effect of the negative photoresist.
In this embodiment, the polymerization inhibitor includes one of phenol, hydroquinone, resorcinol, p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol, and phenothiazine. The catalyst comprises one of triethylamine, triethanolamine, N-dimethylaniline, N-dimethylbenzylamine, triphenylphosphine, benzyltriphenylphosphonium bromide, tetrabutylphosphonium bromide, 2-mercaptobenzothiazole, diazabicyclo or lithium carbonate. The polymerization inhibitor comprises phenol, hydroquinone, resorcinol, p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol or phenothiazine. Preferred p-hydroxyanisole and 2, 6-di-tert-butyl-p-cresol not only provide better polymerization inhibition effect, but also facilitate the complete photocuring of the negative photoresist attached to the bottom of the substrate, and the color of the synthesized negative photoresist resin is light. The catalyst comprises triethylamine, triethanolamine, N-dimethylaniline, N-dimethylbenzylamine, triphenylphosphine, benzyltriphenylphosphonium bromide, tetrabutylphosphonium bromide, 2-mercaptobenzothiazole, diazabicyclo (DBU for short) or lithium carbonate, and preferably adopts a nitrogen-free catalyst, so that the problem of reduction of hydrofluoric acid resistance caused by catalyst residue is avoided.
As shown in fig. 1 and 2, according to another aspect of the present invention, there is also provided a method for preparing the negative photoresist resin, comprising the steps of:
s1, uniformly mixing the monomolecular solid epoxy resin with the high-boiling-point solvent, and heating to fully dissolve the monomolecular solid epoxy resin to obtain a mixed solution A;
s2, adding part of polymerization inhibitor into the mixed solution A obtained in the step S1, and uniformly mixing to obtain mixed solution B;
s3, uniformly mixing the residual polymerization inhibitor, part of catalyst and acryloyl oxypolymethylene carboxylic acid to obtain a mixed solution C, slowly dropwise adding the mixed solution C into the mixed solution B obtained in the step S2, controlling the temperature to be 80-90 ℃, after dropwise adding, heating to 90-100 ℃ for reaction, and obtaining a reaction solution with the acid value of less than or equal to 0.5 mgKOH/g;
s4, adding acid anhydride and the residual catalyst into the reaction liquid obtained in the step S3, controlling the temperature to perform reaction, measuring the acid value to be less than or equal to 90, and cooling to obtain the negative photoresist resin.
The preparation method of the negative photoresist resin comprises the steps of uniformly mixing monomolecular solid epoxy resin with a high-boiling-point solvent to ensure that the monomolecular solid epoxy resin is completely dissolved, adding a part of polymerization inhibitor into a mixed solution A to ensure that the polymerization inhibitor participates in the initial reaction stage and is fully dissolved in the mixed solution A, so that sudden polymerization can be effectively prevented, slowly dropwise adding a mixed solution C containing acryloyloxy polymethylene carboxylic acid into the mixed solution B for reaction, controlling the temperature to be 80-90 ℃, avoiding overhigh temperature in the initial reaction stage and causing sudden polymerization due to overhigh reaction, after the dropwise adding is finished, heating to 90-100 ℃ to ensure that the reaction is completely carried out, and determining the reaction process by taking the acid value of a reaction solution to be less than or equal to 0.5 as a monitoring index; then adding the anhydride and the residual catalyst to finally complete the reaction.
In this embodiment, the heating temperature in step S1 is 80 ℃ to 90 ℃ so that the monomolecular solid epoxy resin can be completely dissolved in the high boiling point solvent; the dripping time of the step S3 is 1.5-2.5 h, the reaction time is 1.5-2.5 h at the temperature of 80-90 ℃, the reaction speed is controlled, and the reaction is ensured to be carried out stably; then heating to 90-100 ℃, reacting for 7-12 h, and fully reacting; the temperature control temperature of the step S4 is 90-100 ℃, the reaction time is 2-3 h, the temperature after temperature reduction is 50-60 ℃, and the temperature reduction treatment avoids the curing of the negative photoresist resin caused by overhigh temperature and insufficient heat dissipation; the too low temperature of cooling can make the reation kettle blowing speed of splendid attire reaction liquid too slow, it is more to persist, consequently guarantees that the temperature after the cooling is 50 ℃ -60 ℃.
According to another aspect of the present invention, there is also provided a negative photoresist comprising the above negative photoresist resin. The negative photoresist is prepared by using negative photoresist resin, the line edge is straight and regular after the negative photoresist is solidified and developed, the negative photoresist has high resolution, and the etched glass or silicon wafer has fine lines.
In the embodiment, the composition comprises the following components in parts by weight: 60 to 75 portions of negative photoresist resin, 15 to 30 portions of organic solvent, 5 to 10 portions of monomer, 1 to 3 portions of photoinitiator, 0.1 to 0.5 portion of flatting agent and 0.5 to 1 portion of black dye.
The organic solvent is dipropylene glycol methyl ether acetate or propylene glycol phenyl ether acetate. The monomer is propoxylated trimethylolpropane triacrylate ((PO) nTMPTA (n is 3-15, containing 3 and 15), tetrahydrofuryl acrylate (THFA), pentaerythritol triacrylate (PET3A), perfluorohexyl ethyl acrylate and dipentaerythritol hexaacrylate (DPHA), the photoinitiator is 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime) (OXE-2), and the leveling agent is BYK 354.
Examples
The materials and equipment used in the following examples are all conventionally commercially available.
Example 1
S1, adding 100 g of triphenol methane triglycidyl ether epoxy resin (with an epoxy value of 0.32) and 57.40 g of diethylene glycol ethyl ether acetate into a four-mouth bottle, uniformly stirring by using a glass stirrer, and heating to control the temperature to 85 ℃ to complete dissolution to obtain a mixed solution A;
s2, adding 0.20 g of p-hydroxyanisole into the mixed solution A in the step S1, and stirring and mixing uniformly to obtain a mixed solution B;
s3, uniformly mixing 0.20 g of p-hydroxyanisole, 0.50 g of benzyltriphenylphosphonium bromide and 59.59 g of 6- (acryloyloxy) hexanoic acid to obtain a mixed solution C, slowly dropwise adding the mixed solution C into the mixed solution B obtained in the step S2, controlling the temperature to be 85 ℃, completing dropwise addition within 2 hours, heating to 95 +/-1 ℃ for reaction for 8 hours, and obtaining a reaction solution with the acid value of less than or equal to 0.5 mgKOH/g;
s4, adding 69.00 g of hexahydrophthalic anhydride and 0.10 g of benzyltriphenylphosphonium bromide into the reaction solution in the step S3, controlling the temperature to be 95 +/-1 ℃ for reaction for 2 hours, measuring the acid value to be 87.49mgKOH/g, and cooling to 60 ℃ to obtain the negative photoresist resin, namely resin A. As shown in fig. 1.
Example 2
S1, adding 100 g of phloroglucinol triglycidyl ether epoxy resin (with an epoxy value of 0.58) and 61.81 g of diethylene glycol ethyl ether acetate into a four-mouth bottle, uniformly stirring by using a glass stirrer, and heating to control the temperature to be 82 ℃ to complete dissolution to obtain a mixed solution A;
s2, adding 0.2 g of p-hydroxyanisole into the mixed solution A in the step S1, and stirring and mixing uniformly to obtain a mixed solution B;
s3, uniformly mixing 0.22 g of p-hydroxyanisole, 0.53 g of benzyl triphenyl phosphonium bromide and 83.6 g of beta-acryloxypropionic acid to obtain a mixed solution C, slowly dropwise adding the mixed solution C into the mixed solution B obtained in the step S2, controlling the temperature to be 82 ℃, completing dropwise addition within 2 hours, heating to 90 +/-1 ℃ and reacting for 8 hours, wherein the acid value of the obtained reaction liquid is less than or equal to 0.5 mgKOH/g;
s4, adding 62.56 g of tetrahydrophthalic anhydride and 0.12 g of benzyltriphenylphosphonium bromide into the reaction solution in the step S3, controlling the temperature to 90 +/-1 ℃ for reaction for 2 hours, measuring the acid value to be 74.64mgKOH/g, and cooling to 55 ℃ to obtain the negative photoresist resin, namely resin B for short.
Example 3
S1, adding 100 g (epoxy value is 0.95) of dicyclopentenyl ether dioxide epoxy resin and 78.90 g of dipropylene glycol methyl ether acetate into a four-mouth bottle, stirring uniformly by using a glass stirrer, heating and controlling the temperature to be 87 ℃ to complete dissolution, and obtaining a mixed solution A;
s2, adding 0.20 g of p-hydroxyanisole into the mixed solution A in the step S1, and stirring and mixing uniformly to obtain a mixed solution B;
s3, uniformly mixing 0.35 g of p-hydroxyanisole, 0.68 g of tetrabutyl phosphonium bromide and 136.95 g of beta-acryloxypropionic acid to obtain a mixed solution C, slowly dropwise adding the mixed solution C into the mixed solution B obtained in the step S2, controlling the temperature to be 87 ℃, completing dropwise addition within 2.5 hours, heating to 98 +/-1 ℃ and reacting for 10 hours, wherein the acid value of the obtained reaction solution is less than or equal to 0.5 mgKOH/g;
s4, adding 78.65 g of hexahydrophthalic anhydride and 0.12 g of tetrabutyl phosphonium bromide into the reaction solution in the step S3, controlling the temperature to be 98 +/-1 ℃ for reaction for 2 hours, measuring the acid value to be 72.55mgKOH/g, and cooling to 58 ℃ to obtain negative photoresist resin, namely resin C for short. As shown in fig. 2.
Example 4
TABLE 1 addition of negative photoresist Components
The rotation speed is 1000 revolutions per minute, the components in the table 1 are sequentially added while stirring, and after uniform mixing, the negative photoresist is dispersed for 30 minutes at the rotation speed of 1500 revolutions per minute to obtain the negative photoresist.
Uniformly printing the glue on a processed flat silicon wafer by using a 2-micron pull rod, baking for 10 minutes at 90 ℃, exposing the glue by using 365nm ultraviolet light through a 100nm grating, developing by using 0.2% sodium carbonate pure water, washing by using the pure water, drying for 10 minutes at 110 ℃, soaking for 5 minutes in a 5% HF pure water solution, washing by using the pure water, and removing the glue by using sodium hydroxide to obtain a photoetching fine pattern.
Example 5
TABLE 2 addition of negative photoresist Components
The rotation speed is 800 revolutions per minute, the components in the table 1 are sequentially added while stirring, and after uniform mixing, the negative photoresist is dispersed for 25 minutes at the rotation speed of 1600 revolutions per minute to obtain the negative photoresist.
Uniformly printing the glue on a processed flat silicon wafer by using a 2-micron pull rod, baking for 12 minutes at 90 ℃, exposing the glue by using 365nm ultraviolet light through a 100nm grating, developing by using 0.2% sodium carbonate pure water, washing by using the pure water, drying for 10 minutes at 110 ℃, soaking for 5 minutes in a 5% HF pure water solution, washing by using the pure water, and removing the glue by using sodium hydroxide to obtain a photoetching fine pattern.
Example 6
TABLE 3 addition of negative photoresist Components
The rotation speed is 600 revolutions per minute, the components in the table 1 are sequentially added while stirring, and after uniform mixing, the negative photoresist is dispersed for 25 minutes at the rotation speed of 2000 revolutions per minute to obtain the negative photoresist.
Uniformly printing the glue on a processed flat silicon wafer by using a 2-micron pull rod, baking for 15 minutes at 90 ℃, exposing the glue by using 365nm ultraviolet light through a 100nm grating, developing by using 0.2% sodium carbonate pure water, washing by using the pure water, drying for 10 minutes at 120 ℃, soaking for 5 minutes in a 5% HF pure water solution, washing by using the pure water, and removing the glue by using sodium hydroxide to obtain a photoetching fine pattern.
Example 7
TABLE 4 addition of negative photoresist Components
The rotation speed is 800 r/min, the components in the table 1 are sequentially added while stirring, and after uniform mixing, the negative photoresist is dispersed for 28 minutes at the rotation speed of 1600 r/min to obtain the negative photoresist.
Uniformly printing the glue on a processed flat silicon wafer by using a 2-micron pull rod, baking for 15 minutes at 90 ℃, exposing the glue by using 365nm ultraviolet light through a 100nm grating, developing by using 0.2% sodium carbonate pure water, washing by using the pure water, drying for 10 minutes at the temperature of 115 ℃, soaking for 5 minutes in a 5% HF pure water solution, washing by using the pure water, and removing the glue by using sodium hydroxide to obtain a photoetching fine pattern.
Comparative example 1
TABLE 5 addition of components of photoresists
The rotation speed is 800 revolutions per minute, the components in the table 1 are sequentially added while stirring, and after uniform mixing, the photoresist is dispersed for 25 minutes at the rotation speed of 1600 revolutions per minute to obtain the photoresist.
Uniformly printing the glue on a processed flat silicon wafer by using a 2-micron pull rod, baking for 12 minutes at 90 ℃, exposing the glue by using 365nm ultraviolet light through a 100nm grating, developing by using 0.2% sodium carbonate pure water, washing by using the pure water, drying for 10 minutes at 110 ℃, soaking for 5 minutes in a 5% HF pure water solution, washing by using the pure water, and removing the glue by using sodium hydroxide to obtain a photoetching fine pattern.
Comparative example 2
TABLE 6 addition of components of photoresists
The rotation speed is 800 revolutions per minute, the components in the table 1 are sequentially added while stirring, and after uniform mixing, the photoresist is dispersed for 25 minutes at the rotation speed of 1600 revolutions per minute to obtain the photoresist.
Uniformly printing the glue on a processed flat silicon wafer by using a 2-micron pull rod, baking for 12 minutes at 90 ℃, exposing the glue by using 365nm ultraviolet light through a 100nm grating, developing by using 0.2% sodium carbonate pure water, washing by using the pure water, drying for 10 minutes at 110 ℃, soaking for 5 minutes in a 5% HF pure water solution, washing by using the pure water, and removing the glue by using sodium hydroxide to obtain a photoetching fine pattern.
The negative resists of examples 4 to 7 and the resists of comparative examples 1 and 2 were subjected to performance tests, and the test results are shown in table 7.
The pencil hardness test standard refers to GB/T6739-2006.
The adhesion test standard refers to GB/T6739-2006.
The resolution detection standard refers to GB/T29556-2013.
The acid resistance test standard refers to GB 1785-79.
TABLE 7 addition of components of photoresists
As can be seen from table 7, the negative photoresist prepared in example 7 has the best overall performance, and compared with the results obtained in comparative examples 1 and 2, the negative photoresist prepared in the present invention has better performances, and meanwhile, the negative photoresist prepared in example 4 has slightly poorer performances than those of other examples, because resin a has a certain influence on the performances of the negative photoresist, the resin performances are slightly poorer than those of other negative photoresists, but the performances of the negative photoresists obtained in examples 4 to 7 are better than those of the photoresists in comparative examples 1 and 2.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A negative photoresist resin comprising, in parts by weight:
20 to 40 parts of monomolecular solid epoxy resin, 15 to 35 parts of acryloyl oxypolymethylene carboxylic acid, 10 to 30 parts of anhydride, 10 to 25 parts of high boiling point solvent, 0.08 to 0.2 part of polymerization inhibitor and 0.1 to 0.3 part of catalyst.
2. The negative photoresist resin according to claim 1,
24 to 40 parts of monomolecular solid epoxy resin, 18 to 34 parts of acryloyl oxypolymethylene carboxylic acid, 15 to 30 parts of anhydride, 16 to 25 parts of high boiling point solvent, 0.08 to 0.2 part of polymerization inhibitor and 0.1 to 0.3 part of catalyst.
3. The negative photoresist resin according to claim 1,
the negative photoresist resin is a monomolecular resin;
the epoxy value of the monomolecular solid epoxy resin is 0.3-0.95, and the monomolecular solid epoxy resin comprises triglycidyl isocyanurate, hydantoin epoxy resin, triphenol methane triglycidyl ether epoxy resin, phloroglucinol triglycidyl ether epoxy resin, trimesic acid triglycidyl ester epoxy resin, dicyclopentadiene dioxide epoxy resin, dicyclopentenyl ether dioxide epoxy resin, isophthalic acid diglycidyl ester epoxy resin and terephthalic acid diglycidyl ester epoxy resin.
4. The negative photoresist resin according to claim 1,
the acryloyloxy polymethylene carboxylic acid includes 6- (acryloyloxy) hexanoic acid or beta-acryloyloxy propionic acid.
5. The negative photoresist resin according to claim 1,
the boiling point of the high-boiling-point solvent is more than or equal to 180 ℃, and the high-boiling-point solvent comprises one of dibasic ester, diethylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, ethylene glycol butyl ether acetate or propylene glycol phenyl ether acetate; and/or
The anhydride comprises one of maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or chlorendic anhydride.
6. The negative photoresist resin according to claim 5, characterized in that;
the polymerization inhibitor comprises one of phenol, hydroquinone, resorcinol, p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol or phenothiazine; and/or
The catalyst comprises one of triethylamine, triethanolamine, N-dimethylaniline, N-dimethylbenzylamine, triphenylphosphine, benzyltriphenylphosphonium bromide, tetrabutylphosphonium bromide, 2-mercaptobenzothiazole, diazabicyclo or lithium carbonate.
7. A method of preparing a negative-type photoresist resin according to any one of claims 1 to 6, comprising the steps of:
s1, uniformly mixing the monomolecular solid epoxy resin with the high-boiling-point solvent, and heating to fully dissolve the monomolecular solid epoxy resin to obtain a mixed solution A;
s2, adding part of polymerization inhibitor into the mixed solution A obtained in the step S1, and uniformly mixing to obtain mixed solution B;
s3, uniformly mixing the residual polymerization inhibitor, part of catalyst and acryloyl oxypolymethylene carboxylic acid to obtain a mixed solution C, slowly dropwise adding the mixed solution C into the mixed solution B obtained in the step S2, controlling the temperature to be 80-90 ℃, after dropwise adding, heating to 90-100 ℃ for reaction, and obtaining a reaction solution with the acid value of less than or equal to 0.5 mgKOH/g;
s4, adding acid anhydride and the residual catalyst into the reaction liquid obtained in the step S3, controlling the temperature to react, measuring the acid value to be less than or equal to 90mgKOH/g, and cooling to obtain the negative photoresist resin.
8. The method of preparing a negative photoresist resin according to claim 7,
the heating temperature of the step S1 is 80-90 ℃;
the dripping time of the step S3 is 1.5-2.5 h, and the reaction time is 7-12 h;
the temperature control temperature of the step S4 is 90-100 ℃, the reaction time is 2-3 h, and the temperature after temperature reduction is 50-60 ℃.
9. A negative photoresist comprising the negative photoresist resin according to any one of claims 1 to 6.
10. The negative photoresist of claim 9, comprising in parts by weight:
60 to 75 portions of negative photoresist resin, 15 to 30 portions of organic solvent, 5 to 10 portions of monomer, 1 to 3 portions of photoinitiator, 0.1 to 0.5 portion of flatting agent and 0.5 to 1 portion of black dye.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939775A (en) * | 2021-03-10 | 2021-06-11 | 珠海君奥新材料科技有限公司 | Oligomer suitable for photocuring inkjet ink and preparation method thereof |
| CN117872680A (en) * | 2024-03-11 | 2024-04-12 | 中节能万润股份有限公司 | Polymer for photoresist bottom anti-reflection coating, preparation method and application |
| CN117872680B (en) * | 2024-03-11 | 2024-05-10 | 中节能万润股份有限公司 | Polymer for photoresist bottom anti-reflection coating, preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6077879A (en) * | 1997-11-11 | 2000-06-20 | Nippon Shokubai Co., Ltd. | Curable resin and resin composition |
| CN101928378A (en) * | 2010-05-12 | 2010-12-29 | 台州新韩电子油墨有限公司 | Photosensitive resin and use thereof for preparing liquid photoimageable solder resist ink |
| CN105086604A (en) * | 2015-07-13 | 2015-11-25 | 深圳市容大感光科技股份有限公司 | Printing ink composition, application thereof and printed circuit board |
| CN105542124A (en) * | 2016-01-26 | 2016-05-04 | 深圳市容大感光科技股份有限公司 | Alkaline-water soluble light-cured resin and preparation method thereof |
| CN106220827A (en) * | 2016-07-29 | 2016-12-14 | 河北晨阳工贸集团有限公司 | A kind of monomer modified epoxy-ester of silyl acrylate and preparation method thereof |
| CN106496522A (en) * | 2016-10-10 | 2017-03-15 | 中科院广州化学有限公司南雄材料生产基地 | A kind of alkali solubility light-cured epoxy acrylate and preparation method and its etching resisting ink |
-
2020
- 2020-08-12 CN CN202010804728.5A patent/CN112011031B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6077879A (en) * | 1997-11-11 | 2000-06-20 | Nippon Shokubai Co., Ltd. | Curable resin and resin composition |
| CN101928378A (en) * | 2010-05-12 | 2010-12-29 | 台州新韩电子油墨有限公司 | Photosensitive resin and use thereof for preparing liquid photoimageable solder resist ink |
| CN105086604A (en) * | 2015-07-13 | 2015-11-25 | 深圳市容大感光科技股份有限公司 | Printing ink composition, application thereof and printed circuit board |
| CN105542124A (en) * | 2016-01-26 | 2016-05-04 | 深圳市容大感光科技股份有限公司 | Alkaline-water soluble light-cured resin and preparation method thereof |
| CN106220827A (en) * | 2016-07-29 | 2016-12-14 | 河北晨阳工贸集团有限公司 | A kind of monomer modified epoxy-ester of silyl acrylate and preparation method thereof |
| CN106496522A (en) * | 2016-10-10 | 2017-03-15 | 中科院广州化学有限公司南雄材料生产基地 | A kind of alkali solubility light-cured epoxy acrylate and preparation method and its etching resisting ink |
Non-Patent Citations (1)
| Title |
|---|
| SHENGYUAN LIANG ET AL.: "Preparation and characterization of dimer fatty acid epoxy-acrylate resin hybrid emulsion for photocurable coatings", 《COLLOID AND POLYMER SCIENCE》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939775A (en) * | 2021-03-10 | 2021-06-11 | 珠海君奥新材料科技有限公司 | Oligomer suitable for photocuring inkjet ink and preparation method thereof |
| CN112939775B (en) * | 2021-03-10 | 2022-10-14 | 珠海君奥新材料科技有限公司 | Oligomer suitable for photocuring inkjet ink |
| CN117872680A (en) * | 2024-03-11 | 2024-04-12 | 中节能万润股份有限公司 | Polymer for photoresist bottom anti-reflection coating, preparation method and application |
| CN117872680B (en) * | 2024-03-11 | 2024-05-10 | 中节能万润股份有限公司 | Polymer for photoresist bottom anti-reflection coating, preparation method and application |
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| CN112011031B (en) | 2022-09-20 |
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