CN108255018B - Photoresist composition comprising poly (p-hydroxystyrene) epoxy resin as film-forming resin - Google Patents
Photoresist composition comprising poly (p-hydroxystyrene) epoxy resin as film-forming resin Download PDFInfo
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- CN108255018B CN108255018B CN201810009674.6A CN201810009674A CN108255018B CN 108255018 B CN108255018 B CN 108255018B CN 201810009674 A CN201810009674 A CN 201810009674A CN 108255018 B CN108255018 B CN 108255018B
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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
Abstract
The present invention relates to a photoresist composition comprising as film-forming resin a polymer of formula (I) wherein Ra‑Rd、Ra0‑Rd0、Ra1‑Rd1、Ra2‑Rd2、n、n0、n1And n2As defined in the specification. When used as a film-forming resin of a photoresist, the film-forming polymer contained in the photoresist composition has the advantages of good ultraviolet light transmission, high viscosity, capability of forming a thick film, high photosensitive speed, high resolution and the like. The photoresist is a negative thick film photoresist which can be applied to advanced packaging technology and MEMS manufacturing, the film thickness of the photoresist can reach 20-100 microns by one-time spin coating according to requirements, the independent line width range of resolution is more than 5 microns, and the sensitivity (measured by the film thickness of 20 microns) is 50-80mJ/cm‑2。
Description
Technical Field
The present invention relates to a photoresist composition comprising a polyhydroxystyrene-based epoxy resin as a film-forming resin. The photoresist composition is suitable for the fields of advanced packaging (silicon chip and packaging WLP) of large-scale integrated circuits and Micro-Electronic mechanical systems (MEMS).
Background
The photoresist is a corrosion-resistant film material with the solubility changed under the irradiation or radiation of light sources such as ultraviolet light, excimer laser, electron beams, ion beams, X rays and the like. Since the invention in the twentieth and fifty years, the photoresist becomes the most core process material in the semiconductor industry, and is widely applied to the manufacture of integrated circuits and printed circuit boards. In the early nineties of the twentieth century, the photoresist is applied to the processing and manufacturing of LCD devices, and plays an important promoting role in large-size, high-precision and colorization of LCD panels. The photoresist also plays a key role in playing a role in the aspect of significance in the process of fine processing from micron level, submicron level and deep submicron level to nanoscale level in the microelectronic manufacturing industry.
The photoresist can be classified into a positive photoresist and a negative photoresist according to the change of the solubility of the photoresist before and after exposure. Positive photoresists have increased solubility upon exposure and development, and negative photoresists have decreased solubility upon exposure and development. In general, positive photoresist has the advantages of high resolution, strong dry etching resistance, good heat resistance, convenient photoresist stripping, good contrast and the like, but has poor adhesion and mechanical strength and higher cost. The negative photoresist has good adhesion capability to a substrate, acid resistance, alkali resistance and high photosensitive speed, but the resolution ratio of the negative photoresist is limited because the negative photoresist is easy to deform and swell during development due to the fact that the dissolution capability is weakened because the negative photoresist is crosslinked in an exposure area.
With the continuous development of high integration and refinement of electronic devices, the requirements on the performances such as photoresist resolution and the like are also continuously improved. The lithography technology has undergone the progression from g-line (436nm) lithography, i-line (365nm) lithography, to KrF (deep ultraviolet 248nm) lithography, ArF (deep ultraviolet 193nm) lithography, and next-generation extreme ultraviolet (EUV, 13.5nm) lithography, and photoresists corresponding to the respective exposure wavelengths have also come into play. The key formula components in the photoresist, such as film-forming resin, are changed, so that the comprehensive performance of the photoresist can better meet the process requirements.
The micro-electromechanical system (MEMS) is a miniaturized mechanical electronic intelligent system, which is composed of three main parts, namely a micro sensor, a micro actuator and a micro energy source, wherein the system size is generally in a micron level or even smaller, and the internal structure size is in a micron level or even nanometer level. The micro-electro-mechanical system has the advantages of miniaturization, intellectualization, integration, multifunction, suitability for batch production and the like, and has wide development prospect in the fields of military, aerospace, information communication, biomedicine, automatic control, automobile industry and the like.
The fabrication of the microstructure of the MEMS device is achieved by a photolithographic process. Unlike the higher resolution of the photolithography process in general integrated circuit fabrication, the higher aspect ratio is sought in MEMS fabrication, which requires a certain thickness of the photoresist used for MEMS. In order to meet the requirements of the development of MEMS products, thick film photoresists are produced. In general, thick film photoresists are required to have good photosensitivity and aspect ratio, with coating thicknesses typically up to at least 10 microns. In the MEMS manufacturing process, the thick glue can be directly used as a working part of an MEMS device, can also be used as a sacrificial layer material to manufacture MEMS devices with a membrane structure and a cantilever beam structure, or can be used as a mask layer of wet etching, and can also be used as an electroplating model to manufacture a three-dimensional MEMS device with non-silicon materials. Therefore, with the continuous development of MEMS, it is important to develop a thick film photoresist suitable for MEMS fabrication.
Currently, commercial thick-film photoresist positive photoresists mainly comprise AZ series positive photoresists, SJR3000 series positive photoresists, Ma-p100 positive photoresists, SPR 220-7 positive photoresists and the like, and the negative photoresists mainly comprise SU-8 series negative photoresists produced by American MicroChem company.
The commercial positive thick film photoresist belongs to diazonaphthoquinone positive photoresist, and mainly comprises phenolic resin, photosensitive compound diazonaphthoquinone and organic solvent. Under the irradiation of ultraviolet light, the diazonaphthoquinone compound in the exposure area is subjected to photolysis reaction, loses one molecule of nitrogen, and is subjected to Wolff rearrangement to be converted into indene carboxylic acid, so that the adhesive film can be dissolved in an alkaline developing solution. In the non-exposed area, photochemical reaction cannot occur, and hydroxyl of the phenolic resin and the diazonaphthoquinone compound form a stable six-membered ring structure through hydrogen bonding, so that the dissolution of the resin is inhibited.
The SU-8 photoresist is an epoxy resin photoresist, and has become the most widely and generally used photoresist in the field of MEMS at present due to good chemical, optical and mechanical properties. The SU-8 photoresist mainly comprises bisphenol A novolac epoxy resin, an organic solvent (gamma-butyrolactone or cyclopentanone) and a small amount of a photo-acid generator triarylsulfonium salt. During exposure, the triarylsulfonium salt absorbs photons to release strong acid, in the post-baking process, the epoxy groups in the acid-catalyzed epoxy resin are subjected to cationic polymerization crosslinking, the crosslinking reaction is increased in a chain manner, a dense crosslinking network structure with large molecular weight can be quickly formed, and the network structure is insoluble in a developing solution in the developing process and is reserved. In the non-exposed area, the photoacid generator can not generate acid, so that the epoxy group can not be catalyzed to polymerize and crosslink, and the resin can be dissolved in a developing solution in the developing process.
The sensitization principle of SU-8 series photoresists is based on cationic photocuring of epoxy resins. The cationic photocuring system is rapidly developed as an important system in the UV curing technology, and compared with a free radical photocuring system, the cationic photocuring system has the most remarkable advantages of no inhibition of oxygen, small curing volume shrinkage, difficult termination of curing reaction, capability of continuing the curing reaction after the illumination is stopped, and low toxicity. Due to these advantages, cationic photocurable materials are well suited as the main component of thick film photoresists.
Currently, cationic photocuring systems are mainly vinyl ether systems, epoxy systems and oxetane systems.
The main advantages of the vinyl ether cation photocuring system are that the curing speed is very fast, no induction period exists, the curing can be carried out at normal temperature, but the curing system has the defects of poor stability and the like, the viscosity is low, and a thick film is not easy to form.
The oxetane photocuring system is a novel cationic photocuring system, can be cured at normal temperature, has low curing shrinkage, thorough curing, high bonding strength and lower viscosity than epoxy monomers, requires larger exposure in the curing process, and has fewer types and higher price at present.
The epoxy system is the most commonly used cationic photocuring system at present, has the advantages of rich monomer types, low price, good adhesiveness after curing, high strength and high viscosity, can reduce the influence of environmental temperature and humidity on curing and has slower curing reaction rate through proper process conditions, and is more suitable for thick-film photoresist film-forming resin. As epoxy systems, mainly comprising novolac epoxy resins, the main performance characteristics of which are the disadvantages as described for the film-forming resins of SU-8 photoresists as described above: the phenolic resin is synthesized by polycondensation, the degree of the polycondensation is not easy to control, the molecular weight distribution of the obtained product is wide, the product needs to be graded and screened, the process flow is complex, the operation is not easy, and the cost is high. If the molecular weight of the resin is not uniform, dissolution in the developer is not uniform, which may affect the resolution of the photoresist.
Another class of film-forming resins for photoresists is the poly-p-hydroxystyrene and its derivatives, the most widely used of which are poly-p-hydroxystyrene with all or part of the hydroxyl groups protected, and the groups commonly used as protecting groups are tert-butyl carbonate, acetals, ketals, silane groups, and the like. This type of photoresist is a positive photoresist whose imaging principle is: in the exposed area, the acid generated by the acid generator catalyzes the film-forming resin to decompose, remove the protecting group and dissolve in the alkaline developing solution, while the resin in the non-exposed area cannot dissolve in the alkaline developing solution due to the existence of the protecting group. The imaging principle of the poly-p-hydroxystyrene photoresist is as follows: in the exposed areas, the acid-catalyzed cross-linking agent and the film-forming resin undergo a cross-linking reaction, rendering the resin insoluble in the developer in the exposed areas and soluble in the developer in the unexposed areas. However, the currently developed poly (p-hydroxystyrene) based photoresists are few in types, and the obtained photoresist is not a thick film photoresist but a common photoresist.
Disclosure of Invention
In view of the problems in the prior art, the inventors of the present invention have conducted extensive and intensive studies on a film-forming resin of a photoresist, and have found a novel photoresist comprising a cation photo-curable film-forming resin, which has advantages of good ultraviolet transmittance, high viscosity, capability of forming a thick film, high photosensitive speed, high resolution, and the like. The present inventors have found that the modified resin obtained by introducing an epoxy moiety to a poly (p-hydroxystyrene) molecule can achieve the aforementioned object. The resin with high molecular weight and narrow molecular weight distribution can be obtained by a cation controllable active polymerization method, and the poly-p-hydroxystyrene has good ultraviolet light permeability, and the characteristics of high molecular weight, narrow molecular weight distribution, good ultraviolet light permeability and the like are beneficial to improving the resolution of the photoresist; a large number of benzene rings exist in the resin structure, and the rigidity of the benzene rings enables the resin to have good anti-etching capability; epoxy groups are introduced into the resin, the epoxy groups can generate cationic photopolymerization, the photosensitive speed is high, and oxygen inhibition is avoided, so that the polymerization reaction is not easy to terminate, the polymerization can be continued in a dark place, a cross-linked network is easy to form in an exposure area, and a high-resolution photoetching pattern is obtained; another advantage of epoxy resins is their high viscosity, so that the resulting films adhere well to the substrate and thicker photoresist films can be obtained. Due to the advantages, the modified resin has good application prospect in the field of thick film photoresist. The present invention has been achieved based on the foregoing findings.
Accordingly, it is an object of the present invention to provide a photoresist composition comprising a modified poly (p-hydroxystyrene) resin containing an epoxy moiety as a film-forming resin. The film-forming resin contained in the photoresist composition has the advantages of good ultraviolet light transmittance, high viscosity, capability of forming a thick film, high photosensitive speed, high resolution and the like.
The technical solution for achieving the above object of the present invention can be summarized as follows:
1. a photoresist composition comprising the following components:
(A) a polymer of the following formula (I) as a film-forming resin:
wherein:
Ra-Rdeach of R, Ra0-Rd0Each of R, Ra1-Rd1Each of (1) and Ra2-Rd2Each of which is independently selected from H, halogen, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C12Cycloalkyl, halo C3-C12Cycloalkyl radical, C3-C12Cycloalkyl radical C1-C2Alkyl, halo C3-C12Cycloalkyl radical C1-C2Alkyl, phenyl C1-C2Alkyl, halophenyl C1-C2A group of alkyl groups;
n and n0Each independently is an integer of 0 to 40, but n + n0Is an integer of 20 to 40; and
n1and n2Each independently of the other is an integer of 0 to 5The number of the first and second groups is,
(B) a photoinitiator;
(C) a solvent, which is one or more selected from the group consisting of: o-xylene, m-xylene, p-xylene, anisole, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, gamma-butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, methyl ethyl ketone, methyl isobutyl ketone;
(D) optionally, n-butylamine; and
(E) optionally, a surfactant.
2. A photoresist composition comprising the following components:
(A) a polymer of formula (I) as defined in item 1 as a film-forming resin;
(B) a photoinitiator;
(C) a solvent, preferably one or more selected from the group consisting of: o-xylene, m-xylene, p-xylene, anisole, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, gamma-butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, methyl ethyl ketone, methyl isobutyl ketone;
(D) optionally, n-butylamine; and
(E) optionally, a surfactant,
provided that at least one of component (D) and component (E) must be included in the photoresist composition.
3. The photoresist composition according to item 1 or 2, where Ra-RdEach of R, Ra0-Rd0Each of R, Ra1-Rd1Each of (1) and Ra2-Rd2Each of which is independently selected from H, fluoro, chloro, bromo, C1-C4Alkyl, chloro C1-C4Alkyl, bromo C1-C4Alkyl radical, C1-C4Alkoxy, chloro C1-C4Alkoxy, bromo C1-C4Alkoxy radical, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl radical, C3-C6Cycloalkylmethyl, halo C3-C6A group of cycloalkylmethyl, phenylmethyl, halophenylmethyl; preferably Ra-Rd、Ra0-Rd0、Ra1-Rd1And Ra2-Rd2Are all H.
4. The photoresist composition according to any one of items 1 to 3, where n and n0Each independently is an integer generally from 0 to 20, preferably from 12 to 18, and n + n0Is an integer of 24 to 36, preferably an integer of 25 to 30.
5. The photoresist composition according to any one of items 1 to 4, where n1And n2Each independently is an integer from 0 to 3, preferably 0; and/or, n1+n2Is an integer of 0 to 3, more preferably 0.
6. The photoresist composition according to any one of items 1 to 5, wherein the film forming resin is selected from polymers 1 to 23.
7. The photoresist composition according to any one of items 1 to 6, wherein the photoresist composition may further comprise a photopolymerizable monomer, preferably the photopolymerizable monomer is one or more selected from the group consisting of: vinyl ether monomers, N-vinyl monomers, epoxy monomers, oxetane monomers, free radical cationic hybrid monomers or mixtures thereof; more preferably, the photopolymerizable monomer is selected from the group consisting of ethylene glycol butyl vinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, trimethylolphenylmethane trivinyl ether, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylimidazole, limonene dioxide, 1, 2-epoxycyclohexane, dicyclopentadiene diepoxide, 1, 4-butanediol diglycidyl ether, 1, 2-epoxy-4-vinylcyclohexane, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 3, 4-epoxycyclohexanecarboxylic acid methyl ester, 3, 4-epoxycyclohexylmethyl ester of 3, 4-epoxycyclohexanecarboxylic acid, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 3-ethyl-3-oxetanemethanol, 3-ethyl-3- [ (2-ethylhexyloxy) methyl ] oxetane, 3' - (oxybis-methylene) -bis- (3-ethyl) oxetane, 1, 4-bis [ 3-ethyl-3-oxymethyleneoxetanyl ] methyl ] benzene, 2- [2- (ethyleneoxy) ethoxy ] ethyl 2-acrylate, 2, 3-epoxypropyl acrylate, (3-ethyl-3-oxetanyl) methyl 2-acrylate, and (3-ethyl-3-oxetanyl) methyl 2-methacrylate.
8. The photoresist composition according to any one of items 1 to 7, wherein the photoinitiator is one or more selected from iodonium salt, sulfonium salt, triazine heterocyclic acid generators and oxime sulfonate photoinitiator; preferably, the iodonium salt acid generator, the sulfonium salt acid generator and the triazine heterocyclic acid generator have the following general formulae (IV), (V) and (VI), respectively:
R1、R2、R3、R4、R5each independently is unsubstituted C6-C10Aryl, or substituted by halogen, nitro, carbonyl, C1-C12Alkyl radical, C1-C12Alkoxy, thiophenyl, phenyl, substituted phenyl substituted C6-C10Aryl, preferably phenyl or naphthyl, or substituted by halogen, nitro, C1-C6Alkyl, substituted phenyl or naphthyl, wherein the substituted phenyl comprises one or more substituents selected from halogen, nitro, C1-C6Alkyl and C1-C6A group of alkoxy groups;
R6、R7and R8Each independently is C1-C12Alkyl radical, C1-C12Alkoxy, halogen substituted C1-C12Alkyl, halogen substituted C1-C12Alkoxy, unsubstituted phenyl or by C1-C12Alkyl and/or C1-C12Alkoxy-substituted phenyl; and
y, Z is a non-nucleophilic anion,for example trifluoromethanesulphonate, BF4 —、ClO4 —、PF6 —、AsF6 —、SbF6 —。
9. The photoresist composition according to item 8, wherein
The photoinitiator is a compound of formula (IV) in which R1And R2Identical or different and selected from the group consisting of: phenyl and quilt C1-C12Alkyl and/or C1-C8Alkoxy-substituted phenyl; and/or
The photoinitiator is a compound of formula (V), wherein R3、R4And R5Identical or different and selected from the group consisting of: phenyl, thiophenyl phenyl; and/or
The photoinitiator is a compound of formula (VI) in which R6、R7And R8Identical or different and selected from the group consisting of: c1-C6Alkyl radical, C1-C6Alkoxy, halogen substituted C1-C6Alkyl, halogen substituted C1-C6Alkoxy, unsubstituted phenyl or by C1-C12Alkyl and/or C1-C12Phenyl substituted by alkoxy, unsubstituted styryl or by a phenyl ring C1-C12Alkyl and/or C1-C12Alkoxy-substituted styryl.
10. The photoresist composition according to any one of items 1 to 7, wherein the photoinitiator is one or more selected from the group consisting of 4- (phenylthio) phenyl diphenylsulfonium hexafluorophosphate, 4- (phenylthio) phenyl diphenylsulfonium hexafluoroantimonate, bis (4- (diphenylsulfonium) phenyl) sulfide bis hexafluorophosphate, bis (4- (diphenylsulfonium) phenyl) sulfide bis hexafluoroantimonate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluoroantimonate, 4-octyloxydiphenyliodonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate, 4-isobutylphenyl.4' -methylphenylidium hexafluorophosphate, 4-isobutylphenyl-4' -methylphenyliodide hexafluoroantimonate, bis (4-dodecylphenyl) iodonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate, 4-octyloxydiphenyliodonium hexafluorophosphate, bis (4-tert-butylbenzene) iodonium hexafluoroantimonate, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3, 4-dimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) - (4-methoxyphenyl) -acetonitrile, (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) -o-methylphenyl-acetonitrile, (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) -phenylacetonitrile.
11. The photoresist composition according to any one of items 2 to 10, wherein the surfactant is one or more selected from the group consisting of: anionic surfactants, cationic surfactants, nonionic surfactants, and zwitterionic surfactants.
12. The photoresist composition according to any one of items 1 to 11, wherein the photoresist composition comprises the following components in parts by weight:
(A)10 to 50 parts, preferably 15 to 45 parts, more preferably 25 to 40 parts of a polymer of formula (I);
(B)1-20 parts, preferably 2-10 parts, more preferably 3-8 parts of a photoinitiator;
(C)20 to 85 parts, preferably 25 to 80 parts, more preferably 30 to 70 parts of a solvent;
(D)0.1 to 10 parts, preferably 0.5 to 5 parts, more preferably 0.8 to 3 parts of n-butylamine; and
(E)0.1 to 10 parts, preferably 0.1 to 5 parts, more preferably 0.1 to 1 part of a surfactant.
These and other objects, features and advantages of the present invention will become readily apparent to those skilled in the art upon consideration of the following specification in conjunction with the invention.
Detailed Description
According to an aspect of the present invention, there is provided a photoresist composition comprising the following components:
(A) a polymer of the following formula (I) as a film-forming resin:
wherein:
Ra-Rdeach of R, Ra0-Rd0Each of R, Ra1-Rd1Each of (1) and Ra2-Rd2Each of which is independently selected from H, halogen, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C12Cycloalkyl, halo C3-C12Cycloalkyl radical, C3-C12Cycloalkyl radical C1-C2Alkyl, halo C3-C12Cycloalkyl radical C1-C2Alkyl, phenyl C1-C2Alkyl, halophenyl C1-C2A group of alkyl groups;
n and n0Each independently is an integer of 0 to 40, but n + n0Is an integer of 20 to 40; and
n1and n2Each independently an integer of 0 to 5,
(B) a photoinitiator;
(C) a solvent, which is one or more selected from the group consisting of: o-xylene, m-xylene, p-xylene, anisole, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, gamma-butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, methyl ethyl ketone, methyl isobutyl ketone;
(D) optionally, n-butylamine; and
(E) optionally, a surfactant.
According to another aspect of the present invention, there is also provided a photoresist composition comprising the following components: (A) a polymer of formula (I) as defined above as a film-forming resin;
(B) a photoinitiator;
(C) a solvent, preferably one or more selected from the group consisting of: o-xylene, m-xylene, p-xylene, anisole, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, gamma-butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, methyl ethyl ketone, methyl isobutyl ketone;
(D) optionally, n-butylamine; and
(E) optionally, a surfactant,
provided that at least one of component (D) and component (E) must be included in the photoresist composition.
In the present invention, Ra-Rd、Ra0-Rd0、Ra1-Rd1And Ra2-Rd2Is a group on a benzene ring. Ra-RdEqual to or different from each other, Ra0-Rd0Equal to or different from each other, Ra1-Rd1Are the same or different from each other, and Ra2-Rd2Are identical or different from each other and are each independently selected from H, halogen, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C12Cycloalkyl, halo C3-C12Cycloalkyl radical, C3-C12Cycloalkyl radical C1-C2Alkyl, halo C3-C12Cycloalkyl radical C1-C2Alkyl, phenyl C1-C2Alkyl, halophenyl C1-C2The radical of an alkyl group. Preferably, R isa-RdEach of R, Ra0-Rd0Each of R, Ra1-Rd1Each of (1) and Ra2-Rd2Each of which is independently selected from H, fluoro, chloro, bromo, C1-C4Alkyl, chloro C1-C4Alkyl, bromo C1-C4Alkyl radical, C1-C4Alkoxy, chloro C1-C4Alkoxy, bromo C1-C4Alkoxy radical, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl radical, C3-C6Cycloalkylmethyl, halo C3-C6Cycloalkylmethyl, phenylmethyl, halophenylmethyl groups. It is particularly preferred that Ra-Rd、Ra0-Rd0、Ra1-Rd1And Ra2-Rd2Are all H. In addition, Ra、Ra0、Ra1And Ra2May be the same or different, preferably the same. Rb、Rb0、Rb1And Rb2May be the same or different, preferably the same. Rc、Rc0、Rc1And Rc2May be the same or different, preferably the same. Rd、Rd0、Rd1And Rd2May be the same or different, preferably the same.
In the present invention, n0、n1And n2Each independently represents the number of structural units of the poly (p-hydroxystyrene) epoxy resin. n and n0Each independently is typically an integer from 0 to 40, preferably an integer from 0 to 20, more preferably an integer from 12 to 18. n + n0It is usually an integer of 20 to 40, preferably an integer of 24 to 36, more preferably an integer of 25 to 30. n is1And n2Each independently is an integer from 0 to 5, preferably an integer from 0 to 3, more preferably 0. n is1+n2Usually an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0.
To obtain the polymers of the formula (I) according to the invention, the polymers of the formula (II) are generally reacted with compounds of the formula (III),
wherein R isa-Rd、Ra0-Rd0、Ra1-Rd1、Ra2-Rd2、n、n0、n1And n2Each as defined for the polymer of formula (I), and X is halogen, preferably chlorine or bromine.
In the present invention, the reaction of the polymer of the formula (II) with the compound of the formula (III) is usually carried out in the presence of a basic catalyst. There is no particular limitation in the choice of the basic catalyst. Preferably, the alkaline catalyst is NaOH, KOH, Na2CO3、K2CO3One or more of (a). It is particularly preferred that the basic catalyst is K2CO3. In the present invention, the reaction of the polymer of formula (II) with the compound of formula (III) is not particularly limited with respect to the amount of the basic catalyst used. Preferably, the polymer of formula (II) and the basic catalyst are used in amounts such that the molar ratio of monomer units comprised by the polymer of formula (II) to the basic catalyst is from 1:0.1 to 1:1. It is particularly preferred that the polymer of formula (II) and the basic catalyst are used in such amounts that the molar ratio of monomer units comprised by the polymer of formula (II) to the basic catalyst is from 1:0.6 to 1:1.
In the present invention, the reaction of the polymer of formula (II) with the compound of formula (III) is generally carried out in such a way that the polymer of formula (II) is reacted sufficiently. Thus, the polymer of formula (II) and the compound of formula (III) are used in such amounts that the molar ratio of the monomer units comprised by the polymer of formula (II) to the compound of formula (III) is generally in the range from 1:1 to 1: 3. Preferably, the polymer of formula (II) and the compound of formula (III) are used in such amounts that the molar ratio of the monomer units comprised by the polymer of formula (II) to the compound of formula (III) is from 1:1.8 to 1: 2.0.
In the present invention, the reaction of the polymer of the formula (II) with the compound of the formula (III) is usually carried out in solution. The solvent is not particularly limited as long as it can dissolve each reactant. Advantageously, the reaction of the polymer of formula (II) with the compound of formula (III) is carried out in the presence of an organic solvent. Preferably, the organic solvent is one or more selected from ethanol, acetone, ethyl acetate, dichloromethane and chloroform. It is particularly preferable that the organic solvent is one selected from ethanol and acetone.
In the present invention, the reaction of the polymer of formula (II) with the compound of formula (III) is conventional in terms of the reaction conditions such as temperature and pressure. Preferably, the reaction is carried out at 0-30 ℃. It is particularly preferred that the reaction is carried out at 25-30 ℃. The reaction time is advantageously from 8 to 10 hours. The reaction pressure is advantageously atmospheric.
The prepared product is subjected to infrared characterization, and 3500cm in an infrared spectrogram is observed-1Whether the polymer of formula (I) of the present invention is obtained is judged by whether the peak of hydroxyl groups before and after the reaction in the vicinity is reduced or even disappeared or the epoxy group is introduced, and1H-NMR confirmed the product structure.
By way of example, the preparation of the polymer of formula (I) by reaction of the polymer of formula (II) with a compound of formula (III) can generally be carried out as follows:
step 1): mixing a polymer of formula (II) and a basic catalyst in a solvent to obtain a mixture;
step 2): slowly dropwise adding a compound shown in the formula (III) into the mixture obtained in the step 1) for reaction; and
step 3): after the reaction is finished, filtering, distilling under reduced pressure to remove the solvent and excessive reactants to obtain a solid, washing, filtering and drying to obtain the polymer shown in the formula (I).
The operation of step 1) may be performed by: adding the polymer of the formula (II) into a solvent, stirring, introducing nitrogen, and adding a basic catalyst to obtain a mixture.
The operation of step 2) may be performed by: slowly adding the compound of the formula (III) dropwise to the mixture obtained in the step 1) at 25 to 30 ℃ and carrying out a reaction for 8 to 10 hours.
The operation of step 3) may be performed by: after the reaction is finished, filtering to remove undissolved basic catalyst and generated inorganic salt, distilling the filtrate under reduced pressure, evaporating the solvent and excessive compound of the formula (III) to obtain solid, washing with water, filtering, and drying to obtain the polymer of the formula (I).
When the polymer shown in the formula (I) is used as film-forming resin of the photoresist, poly-p-hydroxystyrene is used as a main structure, the poly-p-hydroxystyrene is synthesized by addition polymerization, resin with high molecular weight and narrow molecular weight distribution can be obtained by a cation controllable active polymerization method, the poly-p-hydroxystyrene has good ultraviolet light transmittance, and the characteristics of high molecular weight, narrow molecular weight distribution, good ultraviolet light transmittance and the like are favorable for improving the resolution of the photoresist; a large number of benzene rings exist in the resin structure, and the rigidity of the benzene rings enables the resin to have good anti-etching capability; epoxy groups are introduced into the resin, the epoxy groups can generate cationic photopolymerization, the photosensitive speed is high, and oxygen inhibition is avoided, so that the polymerization reaction is not easy to terminate, the polymerization can be continued in a dark place, a cross-linked network is easy to form in an exposure area, and a high-resolution photoetching pattern is obtained; another advantage of epoxy resins is their high viscosity, so that the resulting films adhere well to the substrate and thicker photoresist films can be obtained.
In the invention, the photoresist film-forming resin is one or more polymers shown in a formula (I).
In a particularly preferred embodiment of the invention, the film-forming resin is one or more selected from the group consisting of:
in the photoresist composition of the present invention, the photoinitiator may be any photoinitiator suitable for a photoresist. According to the invention, the photoinitiator is preferably any one or more of iodonium salt, sulfonium salt, triazine heterocyclic acid generators and sulfonic oxime ester photoinitiator. Advantageously, the iodonium salt photoinitiator, the sulfonium salt photoinitiator and the triazine heterocyclic photoinitiator have the following general formulae (IV), (V) and (VI), respectively:
wherein
R1、R2、R3、R4、R5Each independently is unsubstituted C6-C10Aryl, or substituted by halogen, nitro, carbonyl, C1-C12Alkyl radical, C1-C12Alkoxy, thiophenyl, phenyl, substituted phenyl substituted C6-C10Aryl, preferably phenyl or naphthyl, or substituted by halogen, nitro, C1-C6Alkyl, substituted phenyl or naphthyl, wherein the substituted phenyl comprises one or more substituents selected from halogen, nitro, C1-C6Alkyl and C1-C6A group of alkoxy groups;
R6、R7and R8Each independently is C1-C12Alkyl radical, C1-C12Alkoxy, halogen substituted C1-C12Alkyl, halogen substituted C1-C12Alkoxy, unsubstituted phenyl or by C1-C12Alkyl and/or C1-C12Alkoxy-substituted phenyl; and
y, Z are non-nucleophilic anions, e.g. triflate, BF4 —、ClO4 —、PF6 —、AsF6 —、SbF6 —。
In one embodiment of the invention, the photoinitiator is a compound of formula (IV), wherein R1And R2Identical or different and selected from the group consisting of: phenyl and quilt C1-C12Alkyl and/or C1-C8Alkoxy-substituted phenyl.
In one embodiment of the invention, the photoinitiator is a compound of formula (V), wherein R3、R4And R5Identical or different and selected from the group consisting of: phenyl, thiophenyl phenyl.
In one embodiment of the invention, the photoinitiator is a compound of formula (VI) wherein R6、R7And R8Identical or different and selected from the group consisting of: c1-C6Alkyl radical, C1-C6Alkoxy, halogen substituted C1-C6Alkyl, halogen substituted C1-C6Alkoxy, unsubstituted phenyl or by C1-C12Alkyl and/or C1-C12Phenyl substituted by alkoxy, unsubstituted styryl or by a phenyl ring C1-C12Alkyl and/or C1-C12Alkoxy-substituted styryl.
In a particularly preferred embodiment of the present invention, the photoinitiator is one or more selected from the group consisting of 4- (phenylthio) phenyl diphenylsulfonium hexafluorophosphate, 4- (phenylthio) phenyl diphenylsulfonium hexafluoroantimonate, bis (4- (diphenylsulfonium) phenyl) sulfide bis hexafluorophosphate, bis (4- (diphenylsulfonium) phenyl) sulfide bis hexafluoroantimonate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluoroantimonate, 4-octyloxydiphenyliodonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate, 4-isobutylphenyl.4' -methylphenyliodionium hexafluorophosphate, 4-isobutylphenyl-4' -methylphenyliodide hexafluoroantimonate, bis (4-dodecylphenyl) iodonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate, 4-octyloxydiphenyliodonium hexafluorophosphate, bis (4-tert-butylbenzene) iodonium hexafluoroantimonate, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3, 4-dimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) - (4-methoxyphenyl) -acetonitrile, (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) -o-methylphenyl-acetonitrile, (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) -phenylacetonitrile. It is particularly preferred that the photoinitiator is one or more selected from the group consisting of bis (4- (diphenylsulfonium) phenyl) sulfide bishexafluorophosphate, bis (4- (diphenylsulfonium) phenyl) sulfide bishexafluoroantimonate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluoroantimonate, 4-octyloxydiphenyliodonium hexafluoroantimonate, 4-isobutylphenyl.4' -methylphenyliodiium hexafluorophosphate, bis (4-dodecylphenyl) iodonium hexafluoroantimonate, bis (4-dodecylphenyl) iodonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluoroantimonate, 2- (3, 4-dimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) - (4-methoxyphenyl) -acetonitrile, (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) -o-methylphenyl-acetonitrile.
In the photoresist composition of the present invention, the solvent is or preferably is one or more selected from the group consisting of: o-xylene, m-xylene, p-xylene, anisole, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, gamma-butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, methyl ethyl ketone, methyl isobutyl ketone. It is particularly preferable to use, as the solvent, one or more selected from the group consisting of: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, gamma-butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, methyl ethyl ketone and methyl isobutyl ketone.
In the photoresist composition of the present invention, n-butylamine, optionally present, may function as an acid diffusion inhibitor, i.e., to prevent diffusion of acid generated by exposure of the photoresist.
In the photoresist composition of the present invention, anionic, cationic, nonionic and zwitterionic surfactants can be used as the optional surfactant. As anionic surfactants, mention may be made of C10-C18Alkyl sulfates, C8-C18Fatty alcohol ether sulfates, C10-C18Alkyl benzene sulfonate, C8-C18Fatty alcohol ether benzene sulfonate, C10-C18Alkylsulfonic acid salt, C8-C18Fatty alcohol ether sulfonates, polyether siloxane quaternaries, e.g. ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium fatty alcohol ether sulfate, sodium isotridecyl alcohol ether sulfate, C12-C14Sodium fatty alcohol ether sulfate and sodium dodecyl diphenyl ether disulfonate. As the cationic surfactant, CF may be mentioned3(CF2)6CONH(CH2)3N+(CH3)3I-Polysiloxane phosphate, CF3(CF2)2O[CF(CF3)CF2O]2CF(CF3)CONH(CH2)2N+CH3(C2H5)2I-. Mention may be made, as nonionic surfactants, of coconut fatty acid monoethanolamide, coconut fatty acid diethanolamide, C12-14Alkyl glycoside, C12-16Alkyl glycoside, hydroxyl synthetic alcohol polyoxyethylene ether and polyether modified silicone oil. As zwitterionic surfactants, mention may be made of cocamidopropyl betaine, lauryl dimethyl amine oxide, cocamidopropyl dimethyl betaine, fatty alcohol polyoxyethylene ether disodium sulfosuccinate, fatty alcohol (9EO) ether carboxylate, C9F19CH2CH(OH)CH2OC2H5、C8F17CH2CH2SO2N（CH3）CH2CH2OH and polysiloxane betaines.
Preferably, according to the present invention, the photoresist composition may further compriseContaining a photopolymerizable monomer. The photopolymerizable monomer may act as a reactive diluent. As the photopolymerizable monomer, for example, a vinyl ether monomer, an N-vinyl monomer, an epoxy monomer, an oxetane monomer, a radical cationic hybrid monomer, or a mixture thereof can be mentioned. Preferred photopolymerizable monomers are ethylene glycol butyl vinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, trimethylolphenylmethane trivinyl ether, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylimidazole, limonene dioxide, 1, 2-epoxycyclohexane, dicyclopentadiene diepoxide, 1, 4-butanediol diglycidyl ether, 1, 2-epoxy-4-vinylcyclohexane, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, methyl 3, 4-epoxycyclohexanecarboxylate, 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 3-ethyl-3-oxetanemethanol, 3-ethyl-3- [ (2-ethylhexyloxy) methyl]Oxetanes, 3' - (oxybis-methylene) -bis- (3-ethyl) oxetanes
1, 4-bis [ 3-ethyl-3-oxymethyleneoxetanes]Methyl radical]Benzene, 2-acrylic acid 2- [2- (ethyleneoxy) ethoxy]Ethyl ester, 2, 3-epoxypropyl acrylate, 2-acrylic acid (3-ethyl-3-oxetanyl) methyl ester, 2-methacrylic acid (3-ethyl-3-oxetanyl) methyl ester. More preferred photopolymerizable monomers are ethylene glycol butyl vinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, N-vinylcaprolactam, N-vinylpyrrolidone, 1, 2-epoxy-4-vinylcyclohexane, 1, 2-epoxycyclohexane, methyl 3, 4-epoxycyclohexanecarboxylate, 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate, 3-ethyl-3- [ (2-ethylhexyloxy) methyl]Oxetane, 3' - (oxybismethylene) -bis- (3-ethyl) oxetane, 2, 3-epoxypropyl acrylate, (3-ethyl-3-oxetanyl) methyl 2-acrylate, and (3-ethyl-3-oxetanyl) methyl 2-methacrylate.
Preferably, according to the present invention, the photoresist composition may further comprise other basic additives, such as tertiary and/or quaternary amines, more preferably any one or more of triethanolamine, trioctylamine, and tributylamine.
It is preferred according to the present invention that the photoresist composition may further comprise a sensitizer sensitive to a specific wavelength, such as any one or more of 2, 4-diethylthioxanthone, 9-anthracenemethanol and 1- [ (2, 4-xylyl) azo ] -2-naphthol.
In one embodiment of the present invention, the photoresist composition comprises the following components in parts by weight:
(A)10 to 50 parts, preferably 15 to 45 parts, more preferably 25 to 40 parts of a polymer of formula (I);
(B)1-20 parts, preferably 2-10 parts, more preferably 3-8 parts of a photoinitiator;
(C)20 to 85 parts, preferably 25 to 80 parts, more preferably 30 to 70 parts of a solvent;
(D)0.1 to 10 parts, preferably 0.5 to 5 parts, more preferably 0.8 to 3 parts of n-butylamine; and
(E)0.1 to 10 parts, preferably 0.1 to 5 parts, more preferably 0.1 to 1 part of a surfactant.
In a particularly preferred embodiment of the present invention, the photoresist composition comprises the following components in parts by weight:
(A)25-40 parts of a polymer of formula (I);
(B)3-8 parts of a photoinitiator;
(C)30-70 parts of a solvent;
(D)0.8-3 parts of n-butylamine; and
(E)0.1-1 parts of surfactant.
The polymer of formula (I) of the invention is used as film-forming resin of photoresist, which has the advantages that the resin takes poly-p-hydroxystyrene as a main structure, the poly-p-hydroxystyrene is synthesized by addition polymerization, and the resin with high molecular weight and narrow molecular weight distribution can be obtained by a cation controllable active polymerization method; the poly-p-hydroxystyrene has good ultraviolet light transmission, and the high molecular weight, narrow molecular weight distribution and good ultraviolet light transmission are beneficial to improving the resolution of the photoresist. A large number of benzene rings exist in the resin structure, and the rigidity of the benzene rings enables the resin to have good etching resistance. Particularly, compared with other photoresist film-forming resins taking poly-p-hydroxystyrene as a main body, the film-forming resin of the invention introduces epoxy groups, the epoxy groups can generate cationic photopolymerization, the photosensitive speed is high, and oxygen inhibition is avoided, so that the polymerization reaction is not easy to terminate, the polymerization can be continued in a dark place, and a cross-linked network is easy to form in an exposure area, thereby obtaining a high-resolution photoetching pattern; another advantage of epoxy resins is that they have a high viscosity and therefore adhere well to the substrate and allow thicker photoresist films to be obtained. Therefore, the photoresist improves the conditions of film cracking, pattern deformation and even pattern shedding in the bump process and MEMS manufacturing. In addition, the photoresist is a negative thick film photoresist which can be applied to advanced packaging technology and MEMS manufacturing, and the film thickness can reach 20-100 microns through one-time photoresist coating and sheet throwing according to requirements.
Examples
The present invention will be further illustrated with reference to the following examples, which should not be construed as limiting the scope of the invention.
The characterization and detection methods referred to in the following examples are as follows:
1. infrared spectrum characterization method
The infrared spectrum is measured by an IRaffinity Fourier transform infrared spectrometer of Shimadzu corporation, and the scanning range is 4000--1Samples were processed by KBr pellet method.
2.1Method for characterization of H NMR spectra
1H NMR was measured using a Bruker Avame PRX400 NMR spectrometer with chemical shifts in ppm, deuterated chloroform as solvent, tetramethylsilane as internal standard, a scan width of 400MHz, and 16 scans.
3. Ultraviolet absorption spectrum measuring method
Acetonitrile is used as a solvent, a sample is prepared into a solution with the concentration of 30ppm, an Shimadzu UV-2450 UV visible spectrophotometer is used for measuring the ultraviolet absorption spectrum, the measuring wavelength range is 200-400nm, the resolution is 0.1nm, the bandwidth is 0.1-5nm, and the stray light is less than 0.015%.
4. Epoxy value measuring method
The epoxy value of the sample was determined by the hydrochloric acid-acetone method. Accurately weighing about 0.4g of sample, adding the sample into a 250mL closed conical flask, adding 25mL of 0.2mol/L hydrochloric acid acetone solution, shaking up to completely dissolve the sample, standing at room temperature for 2h, adding 3 drops of phenolphthalein reagent, titrating with 0.1mol/L sodium hydroxide-ethanol standard solution until the solution becomes pink, and carrying out blank titration twice according to the same conditions. The volume of sodium hydroxide standard solution required for titration was recorded and the epoxy value of the sample was calculated according to calculation formula (1).
In the formula:
e-epoxy value, mol/100 g;
V1volume of sodium hydroxide-ethanol standard solution consumed for the blank experiment, mL;
V2volume of sodium hydroxide-ethanol standard solution consumed by the sample, mL;
cNaOH-concentration of sodium hydroxide-ethanol standard solution, mol/L;
m-mass of sample, g.
In this context, all "parts" are parts by weight unless otherwise specified.
Preparation examples
Preparation example 1: poly 4- (2 ', 3' -epoxypropoxy) styrene (Polymer 1)
To 50ml of acetone was added 12g of polyparahydroxystyrene (number average molecular weight 3120, n. gtoreq.26) (0.1mol of the repeating unit) as a solvent, and stirred with electric power, nitrogen gas was introduced, and 2.4g of sodium hydroxide (0.06mol) was added. The temperature of the resulting reaction mixture was controlled at 25 ℃, 16.65g of epichlorohydrin (0.18mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 8 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.50 methylene in the epoxide ring; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.69, 7.02; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine, no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1At 910cm, where no hydroxyl group stretching vibration peak was detected-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 226nm, no ultraviolet absorption peak exists above 226nm, and the ultraviolet light transmission property is good above 226 nm.
Epoxy value measurement results: the epoxy value was 0.57mol/100 g.
Preparation example 2: poly 3, 5-dimethyl-4- (2 ', 3' -epoxypropoxy) styrene (Polymer 2)
50ml of ethanol was used as a solvent, and 14.8g of poly-3, 5-dimethyl-4-hydroxystyrene (number average molecular weight 4144, n ═ 28) (0.1mol of the repeating unit) was added to the solvent, and the mixture was stirred with an electric motor, nitrogen gas was introduced, and 5.6g (0.1mol) of potassium hydroxide was added. The temperature of the resulting reaction mixture was controlled at 20 ℃, 18.5g of epichlorohydrin (0.2mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 8 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic numberAccording to the following (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.34 methyl; 2.50 methylene in the epoxide ring; 2.76 methine in the polystyrene chain; 6.63H on the phenyl ring; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine, no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1No hydroxyl stretching vibration peak, 911cm-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 219nm, no ultraviolet absorption peak exists above 219nm, and the ultraviolet light region above 219nm has good light transmittance.
Epoxy value measurement results: the epoxy value was 0.49mol/100 g.
Preparation example 3: poly 3-methoxy-4- (2 ', 3' -epoxypropoxy) styrene (Polymer 3)
50ml of ethyl acetate was taken as a solvent, 15g of poly-3-methoxy-4-hydroxystyrene (number average molecular weight 3900, n ═ 26) (0.1mol of repeating unit) was added to the solvent, and stirring was carried out with electric stirring, nitrogen gas was introduced, and 8.28g of potassium carbonate (0.06mol) was added. The temperature of the resulting reaction mixture was controlled at 30 ℃, 18.5g of epichlorohydrin (0.2mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 10 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 1.33 methyl groups; 2.50 methylene in the epoxide ring; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.58, 6.53; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine; no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1At 914cm, no hydroxyl group stretching vibration peak was detected-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 223nm, no ultraviolet absorption peak exists above 223nm, and good light transmission is realized in an ultraviolet region above 223 nm.
Epoxy value measurement results: the epoxy value was 0.45mol/100 g.
Preparation example 4: poly 3-chloro-4- (2 ', 3' -epoxypropoxy) styrene (polymer 4)
50ml of ethyl acetate was taken as a solvent, 15.4g of poly-3-chloro-4-hydroxystyrene (number average molecular weight 4466, n. cndot. 29) (0.1mol of the repeating unit) was added to the solvent, and stirring was carried out with electric stirring, nitrogen gas was introduced, and 6.36g of sodium carbonate (0.06mol) was added. The temperature of the resulting reaction mixture was controlled at 30 ℃, 16.65g of epichlorohydrin (0.18mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 30 ℃ for 9 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.57,6.70, 6.96; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine; 2.50 methylene in the epoxy ring, no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1At 914cm, no hydroxyl group stretching vibration peak was detected-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 217nm, no ultraviolet absorption peak exists above 217nm, and the ultraviolet region above 217nm has good light transmittance.
Epoxy value measurement results: the epoxy value was 0.47mol/100 g.
Preparation example 5: polymer 5
50ml of ethyl acetate was taken as a solvent, and 14.6g of a block copolymer of 4-hydroxystyrene and 3, 5-dimethyl-4-hydroxystyrene (number average molecular weight 4236, number n of repeating units of 4-hydroxystyrene)1The number of repeating units n in 2,3, 5-dimethyl-4-hydroxystyrene was 27 (0.1mol of repeating units), and the mixture was stirred with electric power, nitrogen gas was introduced, and 6.36g (0.06mol) of sodium carbonate was added. The temperature of the resulting reaction mixture was controlled at 30 ℃, 16.65g of epichlorohydrin (0.18mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 30 ℃ for 9 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.57,6.70, 6.96; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine; 2.50 methylene in the epoxy ring, 3.0 the hydroxyl signal on p-hydroxystyrene was detected and 3.5 the hydroxyl signal on 3, 5-dimethyl-4-hydroxystyrene disappeared.
And (3) partial infrared spectrum result: 3100cm-1-3500cm-1The peak of the stretching vibration of the hydroxyl group is detected and is 914cm-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 217nm, no ultraviolet absorption peak exists above 217nm, and the ultraviolet region above 217nm has good light transmittance.
Epoxy value measurement results: the epoxy value was 0.40mol/100 g.
Preparation example 6: polymer 6
50ml of ethyl acetate was taken as a solvent, 15g of poly-3-methoxy-4-hydroxystyrene (number average molecular weight 4350, number of repeating units n of 3-methoxy-4-hydroxystyrene: 29) (0.1mol of repeating units) was added to the solvent, and stirring was carried out with electric power, nitrogen gas was introduced, and 6.36g (0.06mol) of sodium carbonate was added. The temperature of the resulting reaction mixture was controlled at 30 ℃, 11.96g of epichlorohydrin (0.13mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 30 ℃ for 9 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.76 methine in the polystyrene chain; 3.80 is the methyl peak on the methoxy group, H on the phenyl ring of 6.57,6.70, 6.96; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine; 2.50 methylene in the epoxide ring, a hydroxyl signal was detected at 9.5 and the integrated area of the hydroxyl signal was 2/29 of the area of the hydroxyl signal of the corresponding starting compound.
And (3) infrared spectrum result: 3100cm-1-3500cm-1The peak of the stretching vibration of the hydroxyl group is detected and is 914cm-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 217nm, no ultraviolet absorption peak exists above 217nm, and the ultraviolet region above 217nm has good light transmittance.
Epoxy value measurement results: the epoxy value was 0.49mol/100 g.
Preparation example 7: polymer 7
50ml of ethyl acetate was taken as a solvent, 15.4g of poly-3-chloro-4-hydroxystyrene (number average molecular weight 4620, n. cndot. 30) (0.1mol of the repeating unit) was added to the solvent, and stirring was carried out with electric stirring, nitrogen gas was introduced, and 6.36g of sodium carbonate (0.06mol) was added. The temperature of the resulting reaction mixture was controlled at 30 ℃, 12.95g of epichlorohydrin (0.14mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 30 ℃ for 9 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.57,6.70, 6.96; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine; 2.50 methylene in the epoxide ring, a hydroxyl signal was detected at 9.5 and the integrated area of the hydroxyl signal was reduced to one tenth of the area of the corresponding starting compound hydroxyl signal.
And (3) infrared spectrum result: 3100cm-1-3500cm-1The peak of the stretching vibration of the hydroxyl group is detected and is 914cm-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 217nm, no ultraviolet absorption peak exists above 217nm, and the ultraviolet region above 217nm has good light transmittance.
Epoxy value measurement results: the epoxy value was 0.40mol/100 g.
Preparation example 8: polymer 8
50ml of acetone was taken as a solvent, 15.6g of poly-3, 5-difluoro-4-hydroxystyrene (number average molecular weight 4680, n. multidot.30) (0.1mol of the repeating unit) was added to the solvent, and stirring was carried out with electric motor, nitrogen gas was introduced, and 2.4g of sodium hydroxide (0.06mol) was added. The temperature of the resulting reaction mixture was controlled at 25 ℃, 16.65g of epichlorohydrin (0.18mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 8 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.50 methylene in the epoxide ring; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.69, 7.02; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine, no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1At 910cm, where no hydroxyl group stretching vibration peak was detected-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 226nm, no ultraviolet absorption peak exists above 226nm, and the ultraviolet light transmission property is good above 226 nm.
Epoxy value measurement results: the epoxy value was 0.57mol/100 g.
Preparation example 9: polymer 9
50ml of acetone was taken as a solvent, 16g of poly (3-isopropyl-5-fluoro-4-hydroxystyrene) (number average molecular weight 4800, n. gtoreq.30) (0.1mol of repeating unit) was added to the solvent, and stirring was carried out with electric stirring, nitrogen gas was introduced, and 2.4g of sodium hydroxide (0.06mol) was added. The temperature of the resulting reaction mixture was controlled at 25 ℃, 16.65g of epichlorohydrin (0.18mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 8 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.2 methyl peak in isopropyl, 1.87 methylene in polystyrene chain; 2.50 epoxy ring of MediaA methyl group; 2.76 methine in the polystyrene chain; 3.05 methine in isopropyl; h on the phenyl ring of 6.69, 7.02; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine, no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1At 910cm, where no hydroxyl group stretching vibration peak was detected-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 226nm, no ultraviolet absorption peak exists above 226nm, and the ultraviolet light transmission property is good above 226 nm.
Epoxy value measurement results: the epoxy value was 0.55mol/100 g.
Preparation example 10: polymer 10
50ml of acetone was taken as a solvent, 20.2g of poly-3-cyclohexyl-4-hydroxystyrene (number average molecular weight 5050, n ═ 25) (0.1mol of the repeating unit) was added to the solvent, stirring was carried out with electric stirring, nitrogen gas was introduced, and 2.4g of sodium hydroxide (0.06mol) was added. The temperature of the resulting reaction mixture was controlled at 25 ℃, 16.65g of epichlorohydrin (0.18mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 8 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.2-2 cyclohexyl multiplets are peaks on cyclohexyl, 1.87 methylene in the polystyrene chain; 2.50 methylene in the epoxide ring; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.69, 7.02; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 2.9 is cyclohexyl last methyl; 3.04 epoxy ring methine, no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1No hydroxy group stretching was detectedVibration peak, 910cm-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 226nm, no ultraviolet absorption peak exists above 226nm, and the ultraviolet light transmission property is good above 226 nm.
Epoxy value measurement results: the epoxy value was 0.58mol/100 g.
Preparation example 11: polymer 11
50ml of ethyl acetate was taken as a solvent, 20.8g of poly (3- (2-chlorocyclopropylmethyl) -4-hydroxystyrene) (number average molecular weight 5824, n. cndot.28) (0.1mol of the repeating unit) was added to the solvent, the mixture was stirred with an electric motor, nitrogen was introduced, and 8.28g of potassium carbonate (0.06mol) was added. The temperature of the resulting reaction mixture was controlled at 30 ℃, 18.5g of epichlorohydrin (0.2mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 10 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.50 methylene in the epoxide ring; 2.54 methylene in cyclopropyl, 2.66 methylene in cyclopropyl; 2.76 methine in the polystyrene chain; 3.0 methylene to cyclopropyl; h on the phenyl ring of 6.58, 6.53; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine; no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1At 914cm, no hydroxyl group stretching vibration peak was detected-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 230nm, no ultraviolet absorption peak exists above 240nm, and good light transmission is realized in an ultraviolet region above 240 nm.
Epoxy value measurement results: the epoxy value was 0.48mol/100 g.
Preparation example 12: polymer 12
50ml of ethyl acetate was taken as a solvent, 21g of poly-3-benzyl-4-hydroxystyrene (number average molecular weight 5880, n. multidot.28) (0.1mol of the repeating unit) was added to the solvent, and stirring was carried out with electric stirring, nitrogen gas was introduced, and 8.28g of potassium carbonate (0.06mol) was added. The temperature of the resulting reaction mixture was controlled at 30 ℃, 18.5g of epichlorohydrin (0.2mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 10 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.50 methylene in the epoxide ring; 2.54 methylene groups attached to the benzene ring; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.58, 6.53; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine; no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1At 914cm, no hydroxyl group stretching vibration peak was detected-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 240nm, no ultraviolet absorption peak exists above 260nm, and good light permeability exists in an ultraviolet region above 260 nm.
Epoxy value measurement results: the epoxy value was 0.40mol/100 g.
Preparation example 13: polymer 13
To 50ml of acetone was added 19.2g of poly (3-isopropyl-5-methoxy-4-hydroxystyrene) (number average molecular weight 5760, n. cndot.30) (0.1mol of the repeating unit) as a solvent, and the mixture was stirred with an electric motor, purged with nitrogen, and added 2.4g (0.06mol) of sodium hydroxide. The temperature of the resulting reaction mixture was controlled at 25 ℃, 16.65g of epichlorohydrin (0.18mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 8 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.2 methyl peak in isopropyl, methyl peak in 1.5 methoxy, methylene in 1.87 polystyrene chain; 2.50 methylene in the epoxide ring; 2.76 methine in the polystyrene chain; 3.05 methine in isopropyl; h on the phenyl ring of 6.69, 7.02; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine, no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1At 910cm, where no hydroxyl group stretching vibration peak was detected-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 234nm, no ultraviolet absorption peak exists above 245nm, and good light transmission is realized in an ultraviolet region above 245 nm.
Epoxy value measurement results: the epoxy value was 0.45mol/100 g.
Preparation example 14: polymer 14
50ml of acetone was taken as a solvent, 19g of poly (3-isopropyl-5-ethyl-4-hydroxystyrene) (number average molecular weight 5700, n. multidot.30) (0.1mol of repeating unit) was added to the solvent, and the mixture was stirred with an electric motor, nitrogen was introduced, and 2.4g (0.06mol) of sodium hydroxide was added. The temperature of the resulting reaction mixture was controlled at 25 ℃, 16.65g of epichlorohydrin (0.18mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 8 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.2 methyl peak in isopropyl; 1.5 methyl peak in ethyl, methylene peak in 1.65 ethyl; 1.87 methylene in the polystyrene chain; 2.50 methylene in the epoxide ring; 2.76 methine in the polystyrene chain; 3.05 methine in isopropyl; h on the phenyl ring of 6.69, 7.02; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine, no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1At 910cm, where no hydroxyl group stretching vibration peak was detected-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 234nm, no ultraviolet absorption peak exists above 245nm, and good light transmission is realized in an ultraviolet region above 245 nm.
Epoxy value measurement results: the epoxy value was 0.45mol/100 g.
Preparation example 15: polymer 15
50ml of acetone was taken as a solvent, 17.8g of poly-3-ethyl-5-methoxy-4-hydroxystyrene (number average molecular weight 4450, n. cndot. 25) (0.1mol of repeating unit) was added to the solvent, and stirring was carried out with electric stirring, nitrogen gas was introduced, and 2.4g of sodium hydroxide (0.06mol) was added. The temperature of the resulting reaction mixture was controlled at 25 ℃, 16.65g of epichlorohydrin (0.18mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 8 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.2 methyl peak in methoxy; 1.5 methyl peak in ethyl, methylene peak in 1.65 ethyl; 1.87 methylene in the polystyrene chain; 2.50 methylene in the epoxide ring; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.69, 7.02; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine, no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1At 910cm, where no hydroxyl group stretching vibration peak was detected-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 230nm, no ultraviolet absorption peak exists above 245nm, and good light transmission is realized in an ultraviolet region above 245 nm.
Epoxy value measurement results: the epoxy value was 0.45mol/100 g.
Preparation example 16: poly 4- (2 ', 3' -epoxypropoxy) styrene (Polymer 16)
To 50ml of acetone was added 12g of polyparahydroxystyrene (number average molecular weight 3000, n. cndot. 25) (0.1mol of repeating unit) as a solvent, and stirred with electric power, nitrogen gas was introduced, and 2.4g of sodium hydroxide (0.06mol) was added. The temperature of the resulting reaction mixture was controlled at 25 ℃, 16.65g of epichlorohydrin (0.18mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 8 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.50 methylene in the epoxide ring; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.69, 7.02; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine, no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1At 910cm, where no hydroxyl group stretching vibration peak was detected-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 226nm, no ultraviolet absorption peak exists above 226nm, and the ultraviolet light transmission property is good above 226 nm.
Epoxy value measurement results: the epoxy value was 0.57mol/100 g.
Preparation example 17: poly 3, 5-dimethyl-4- (2 ', 3' -epoxypropoxy) styrene (Polymer 17)
50ml of ethanol was used as a solvent, and 14.8g of poly-3, 5-dimethyl-4-hydroxystyrene (number average molecular weight: 2960, n ═ 20) (0.1mol of the repeating unit) was added to the solvent, and the mixture was stirred with an electric motor, nitrogen gas was introduced, and 5.6g (0.1mol) of potassium hydroxide was added. The temperature of the resulting reaction mixture was controlled at 20 ℃, 18.5g of epichlorohydrin (0.2mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 8 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.34 methyl; 2.50 methylene in the epoxide ring; 2.76 methine in the polystyrene chain; 6.63H on the phenyl ring; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine, no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1No hydroxyl stretching vibration peak, 911cm-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 219nm, no ultraviolet absorption peak exists above 219nm, and the ultraviolet light region above 219nm has good light transmittance.
Epoxy value measurement results: the epoxy value was 0.49mol/100 g.
Preparation example 18: poly 3-ethoxy-4- (2 ', 3' -epoxypropoxy) styrene (polymer 18)
50ml of ethyl acetate was taken as a solvent, 16.4g of poly-3-ethoxy-4-hydroxystyrene (number average molecular weight 4920, n. multidot.30) (0.1mol of the repeating unit) was added to the solvent, and stirring was carried out with electric stirring, nitrogen gas was introduced, and 8.28g of potassium carbonate (0.06mol) was added. The temperature of the resulting reaction mixture was controlled at 30 ℃, 18.5g of epichlorohydrin (0.2mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 10 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 1.33 methyl groups; 3.98 methylene in the ethoxy radical; 2.50 methylene in the epoxide ring; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.58, 6.53; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine; no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1At 914cm, no hydroxyl group stretching vibration peak was detected-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 223nm, no ultraviolet absorption peak exists above 223nm, and good light transmission is realized in an ultraviolet region above 223 nm.
Epoxy value measurement results: the epoxy value was 0.45mol/100 g.
Preparation example 19: poly 2-chloro-4- (2 ', 3' -epoxypropoxy) styrene (Polymer 19)
50ml of ethyl acetate was taken as a solvent, 15.5g of poly-2-chloro-4-hydroxystyrene (number average molecular weight 3862, n. cndot. 25) (0.1mol of the repeating unit) was added to the solvent, and stirring was carried out with electric stirring, nitrogen gas was introduced, and 6.36g of sodium carbonate (0.06mol) was added. The temperature of the resulting reaction mixture was controlled at 30 ℃, 16.65g of epichlorohydrin (0.18mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 30 ℃ for 9 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.57,6.70, 6.96; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine; 2.50 methylene in the epoxy ring, no hydroxyl signal was detected.
And (3) infrared spectrum result: 3100cm-1-3500cm-1At 914cm, no hydroxyl group stretching vibration peak was detected-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 217nm, no ultraviolet absorption peak exists above 217nm, and the ultraviolet region above 217nm has good light transmittance.
Epoxy value measurement results: the epoxy value was 0.47mol/100 g.
Preparation example 20: poly 2-chloromethyl-4- (2 ', 3' -epoxypropoxy) styrene (polymer 20)
50ml of methylene chloride was taken as a solvent, 17g of poly-2-chloromethyl-4-hydroxystyrene (number average molecular weight 5055, n ═ 30) (0.1mol of the repeating unit) was added to the solvent, and stirring was carried out with electric stirring, nitrogen gas was introduced, and 2.4g of sodium hydroxide (0.06mol) was added. The temperature of the resulting reaction mixture was controlled at 30 ℃, 16.65g of epichlorohydrin (0.18mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 8 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.70, 7.02; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine; 4.64 chloromethyl; 2.50 methylene in the epoxide ring; a weak hydroxyl peak was detected at 5.07.
And (3) infrared spectrum result: 3100cm-1-3500cm-1Detect weak hydroxyl stretching vibration peak at 914cm-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 224nm, no ultraviolet absorption peak exists above 224nm, and good light transmittance is realized in an ultraviolet region above 224 nm.
Epoxy value measurement results: the epoxy value was 0.40mol/100 g.
Preparation example 21: poly 2-methyl-5-methoxy-4- (2 ', 3' -epoxypropoxy) styrene (polymer 21)
50ml of acetone was taken as a solvent, 16.4g of poly-2-methyl-5-methoxy-4-hydroxystyrene (number average molecular weight 5740, n. cndot. 35) (0.1mol of repeating unit) was added to the solvent, and stirring was carried out with electric stirring, nitrogen was introduced, and 11.04g of potassium carbonate (0.08mol) was added. The temperature of the resulting reaction mixture was controlled at 30 ℃, 17.58g of epichlorohydrin (0.19mol) was slowly added dropwise through an isopiestic dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 8 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.38, 6.41; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine; 2.35 methyl; 3.73 methoxy; 2.50 methylene in the epoxide ring, a weak hydroxyl peak was detected at 5.03.
And (3) infrared spectrum result: 3100cm-1-3500cm-1A weak hydroxyl stretching vibration peak of 910cm is detected-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 218nm, no ultraviolet absorption peak exists above 218nm, and good light transmission is realized in an ultraviolet region above 218 nm.
Epoxy value measurement results: the epoxy value was 0.40mol/100 g.
Preparation example 22: poly 3-cyclopropyl-4- (2 ', 3' -epoxypropoxy) styrene (polymer 22)
50ml of acetone was taken as a solvent, 16g of poly-3-cyclopropyl-4-hydroxystyrene (number average molecular weight 6400, n. multidot.40) (0.1mol of the repeating unit) was added to the solvent, and the mixture was stirred with an electric motor, purged with nitrogen, and 4.2g of potassium hydroxide (0.075mol) was added thereto. The temperature of the resulting reaction mixture was controlled at 30 ℃, 17.58g of epichlorohydrin (0.19mol) was slowly added dropwise through an isopiestic dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 9 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.89,6.84, 6.61; 4.07 OxypropoxyMethylene linked to oxygen in the radical; 3.04 epoxy ring methine; 2.50 methylene in the epoxide ring, 1.51 methine in the cyclopropyl group; 0.51 methylene in the cyclopropyl group; a very small hydroxyl peak was detected at 5.41.
And (3) infrared spectrum result: 3100cm-1-3500cm-1Detects a weak hydroxyl stretching vibration peak at 912cm-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 226nm, no ultraviolet absorption peak exists above 226nm, and the ultraviolet light transmission property is good above 226 nm.
Epoxy value measurement results: the epoxy value was 0.42mol/100 g.
Preparation example 23: poly 2-chloro-5-ethoxy-4- (2 ', 3' -epoxypropoxy) styrene (polymer 23)
50ml of ethanol was used as a solvent, 19.85g of poly-2-chloro-5-ethoxy-4-hydroxystyrene (number average molecular weight 6948, n. quadrature.35) (0.1mol of repeating units) was added to the solvent, and stirring was carried out with electric stirring, nitrogen gas was introduced, and 8.48g of sodium carbonate (0.08mol) was added. The temperature of the resulting reaction mixture was controlled at 30 ℃, 18.5g of epichlorohydrin (0.2mol) was slowly added dropwise through a constant pressure dropping funnel over 0.5h, and then the resulting reaction mixture was reacted at 25 ℃ for 10 h. After the reaction was complete, undissolved inorganic material was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and excess epichlorohydrin, to give a solid, which was washed three times with water, filtered and dried to give the title polymer upon analysis.
Nuclear magnetic data as follows (d-CDCl)3): 1.87 methylene in the polystyrene chain; 2.76 methine in the polystyrene chain; h on the phenyl ring of 6.47, 6.59; 4.07 the methylene group of the glycidoxy group bonded to oxygen; 3.04 epoxy ring methine; 2.50 methylene in the epoxide ring, 1.33 methyl in the ethoxy group; 3.98 methylene in the ethoxy radical; a weak hydroxyl peak was detected at 5.13.
And (3) infrared spectrum result: 3100cm-1-3500cm-1The weak hydroxyl group stretching vibration peak is detected at 909cm-1A characteristic absorption peak of the epoxy ring was detected.
Ultraviolet absorption spectrum results: the maximum absorption wavelength is 220nm, no ultraviolet absorption peak exists above 220nm, and good light permeability exists in an ultraviolet region above 220 nm.
Epoxy value measurement results: the epoxy value was 0.37mol/100 g.
Lithography test
Preparing glue: the film-forming resin of the photoresist, the photoinitiator, the solvent, the polymerizable monomer, n-butylamine, and 0.12 part of the surfactant were mixed together according to the formulations shown in tables 1 and 3 below to obtain a solution, stirred for 24 hours, and then filtered through a 0.45 micron film to obtain each photoresist.
TABLE 1
Photoetching: respectively coating the photoresist on 6-inch monocrystalline silicon wafers through spin coating (rotating speed of 3000 r/min), baking for 15 minutes at 105 ℃, cooling to room temperature, then placing the coated silicon wafers in a g-line or i-line mixed exposure machine for exposure, baking for 2 minutes at 100 ℃ after exposure is finished, and developing for 50 seconds at 25 ℃ by using propylene glycol methyl ether acetate aqueous solution as a developing solution (volume ratio of propylene glycol methyl ether acetate: water is 3:1) to obtain a photoetching image. The lithographic parameters for photoresists 1-23 and comparative examples are detailed in table 2.
TABLE 2
It should be noted that the compounding, lithography and all operations involving photoinitiators must be performed under yellow light to prevent failure of the exposure.
The results of the photolithography for each photoresist are shown in Table 3 below. TABLE 3
Claims (26)
1. A photoresist composition comprising the following components:
(A) a polymer of the following formula (I) as a film-forming resin:
wherein:
Ra-Rdeach of R, Ra0-Rd0Each of R, Ra1-Rd1Each of (1) and Ra2-Rd2Each of which is independently selected from H, halogen, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C12Cycloalkyl, halo C3-C12Cycloalkyl radical, C3-C12Cycloalkyl radical C1-C2Alkyl, halo C3-C12Cycloalkyl radical C1-C2Alkyl, phenyl C1-C2Alkyl, halophenyl C1-C2A group of alkyl groups;
n and n0Each independently is an integer of 0 to 40, but n + n0Is an integer of 20 to 40; and
n1and n2Each independently an integer of 0 to 5,
(B) a photoinitiator;
(C) a solvent, which is one or more selected from the group consisting of: o-xylene, m-xylene, p-xylene, anisole, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, gamma-butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, methyl ethyl ketone, methyl isobutyl ketone;
(D) optionally, n-butylamine; and
(E) optionally, a surfactant.
2. A photoresist composition comprising the following components:
(A) a polymer of formula (I) as defined in claim 1 as a film-forming resin;
(B) a photoinitiator;
(C) a solvent;
(D) optionally, n-butylamine; and
(E) optionally, a surfactant,
provided that at least one of component (D) and component (E) must be included in the photoresist composition.
3. The photoresist composition according to claim 2, where the solvent is one or more selected from the group consisting of: o-xylene, m-xylene, p-xylene, anisole, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, gamma-butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, methyl ethyl ketone, methyl isobutyl ketone.
4. The photoresist composition according to claim 1, where Ra-RdEach of R, Ra0-Rd0Each of R, Ra1-Rd1Each of (1) and Ra2-Rd2Each of which is independently selected from H, fluoro, chloro, bromo, C1-C4Alkyl, chloro C1-C4Alkyl, bromo C1-C4Alkyl radical, C1-C4Alkoxy, chloro C1-C4Alkoxy, bromo C1-C4Alkoxy radical, C3-C6Cycloalkyl, halo C3-C6A cycloalkyl group, a,C3-C6Cycloalkylmethyl, halo C3-C6Cycloalkylmethyl, phenylmethyl, halophenylmethyl groups.
5. The photoresist composition according to claim 4, where Ra-Rd、Ra0-Rd0、Ra1-Rd1And Ra2-Rd2Are all H.
6. The photoresist composition according to claim 2, where Ra-RdEach of R, Ra0-Rd0Each of R, Ra1-Rd1Each of (1) and Ra2-Rd2Each of which is independently selected from H, fluoro, chloro, bromo, C1-C4Alkyl, chloro C1-C4Alkyl, bromo C1-C4Alkyl radical, C1-C4Alkoxy, chloro C1-C4Alkoxy, bromo C1-C4Alkoxy radical, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl radical, C3-C6Cycloalkylmethyl, halo C3-C6Cycloalkylmethyl, phenylmethyl, halophenylmethyl groups.
7. The photoresist composition according to claim 6, where Ra-Rd、Ra0-Rd0、Ra1-Rd1And Ra2-Rd2Are all H.
8. The photoresist composition according to any one of claims 1 to 7, where n and n0Each independently is an integer of 0 to 20, and n + n0Is an integer of 24-36.
9. The photoresist composition according to claim 8, where n and n0Each independently an integer from 12 to 18.
10. According toThe photoresist composition of claim 8, where n + n0Is an integer of 25 to 30.
11. The photoresist composition according to any one of claims 1 to 7, where n1And n2Each independently is an integer from 0 to 3; and/or, n1+n2Is an integer of 0 to 3.
12. The photoresist composition according to claim 11, where n is1And n2Is 0.
13. The photoresist composition according to any one of claims 1 to 7, wherein the film forming resin is one or more selected from the group consisting of:
14. the photoresist composition according to any one of claims 1 to 7, wherein the photoresist composition further comprises a photopolymerizable monomer.
15. The photoresist composition according to claim 14, wherein the photopolymerizable monomer is one or more selected from the group consisting of: vinyl ether monomers, N-vinyl monomers, epoxy monomers, oxetane monomers, free radical cationic hybrid monomers or mixtures thereof.
16. The photoresist composition according to claim 14, wherein the photopolymerizable monomer is selected from the group consisting of ethylene glycol butyl vinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, trimethylolphenylmethane trivinyl ether, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylimidazole, limonene dioxide, 1, 2-epoxycyclohexane, dicyclopentadiene diepoxide, 1, 4-butanediol diglycidyl ether, 1, 2-epoxy-4-vinylcyclohexane, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 3, 4-epoxycyclohexanecarboxylic acid methyl ester, 3, 4-epoxycyclohexanecarboxylic acid 3, 4-epoxycyclohexylmethyl ester, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 3-ethyl-3-oxetanemethanol, 3-ethyl-3- [ (2-ethylhexyloxy) methyl ] oxetane, 3' - (oxybis-methylene) -bis- (3-ethyl) oxetane, 1, 4-bis [ 3-ethyl-3-oxymethyleneoxetanyl ] methyl ] benzene, 2- [2- (ethyleneoxy) ethoxy ] ethyl 2-acrylate, 2, 3-epoxypropyl acrylate, (3-ethyl-3-oxetanyl) methyl 2-acrylate, and (3-ethyl-3-oxetanyl) methyl 2-methacrylate.
17. The photoresist composition according to any one of claims 1 to 7, wherein the photoinitiator is one or more selected from iodonium salt, sulfonium salt, triazine heterocyclic acid generators and oxime sulfonate photoinitiators.
18. The photoresist composition according to claim 17, wherein the iodonium salt acid generator, the sulfonium salt acid generator and the triazine heterocyclic acid generator have the following general formulae (IV), (V) and (VI), respectively:
R1、R2、R3、R4、R5each independently is unsubstituted C6-C10Aryl, or substituted by halogen, nitro, carbonyl, C1-C12Alkyl radical, C1-C12Alkoxy, thiophenyl, phenyl,Substituted phenyl-substituted C6-C10Aryl, wherein the substituted phenyl comprises one or more substituents selected from the group consisting of halogen, nitro, C1-C6Alkyl and C1-C6A group of alkoxy groups;
R6、R7and R8Each independently is C1-C12Alkyl radical, C1-C12Alkoxy, halogen substituted C1-C12Alkyl, halogen substituted C1-C12Alkoxy, unsubstituted phenyl or by C1-C12Alkyl and/or C1-C12Alkoxy-substituted phenyl; and
y, Z are non-nucleophilic anions.
19. The photoresist composition according to claim 18, where R1、R2、R3、R4、R5Each independently of the other being phenyl or naphthyl, or by halogen, nitro, C1-C6Alkyl, substituted phenyl or naphthyl, wherein the substituted phenyl comprises one or more substituents selected from halogen, nitro, C1-C6Alkyl and C1-C6A radical of an alkoxy group.
20. The photoresist composition according to claim 18, where Y, Z is triflate, BF4 -、ClO4 -、PF6 -、AsF6 -Or SbF6 -。
21. The photoresist composition according to claim 18, where
The photoinitiator is a compound of formula (IV) in which R1And R2Identical or different and selected from the group consisting of: phenyl and quilt C1-C12Alkyl and/or C1-C8Alkoxy-substituted phenyl; and/or
The photoinitiator is a compound of formula (V), wherein R3、R4And R5Identical or different and selected from the group consisting of: phenyl, thiophenyl phenyl; and/or
The photoinitiator is a compound of formula (VI) in which R6、R7And R8Identical or different and selected from the group consisting of: c1-C6Alkyl radical, C1-C6Alkoxy, halogen substituted C1-C6Alkyl, halogen substituted C1-C6Alkoxy, unsubstituted phenyl or by C1-C12Alkyl and/or C1-C12Phenyl substituted by alkoxy, unsubstituted styryl or by a phenyl ring C1-C12Alkyl and/or C1-C12Alkoxy-substituted styryl.
22. The photoresist composition according to any one of claims 1 to 7, wherein the photoinitiator is one or more selected from the group consisting of 4- (phenylthio) phenyl diphenylsulfonium hexafluorophosphate, 4- (phenylthio) phenyl diphenylsulfonium hexafluoroantimonate, bis (4- (diphenylsulfonium) phenyl) sulfide bis hexafluorophosphate, bis (4- (diphenylsulfonium) phenyl) sulfide bis hexafluoroantimonate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluoroantimonate, 4-octyloxydiphenyliodonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate, 4-isobutylphenyl 4' -methylphenylidium hexafluorophosphate, 4-isobutylphenyl 4' -methylphenyliodide hexafluoroantimonate, bis (4-dodecylbenzene) iodonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate, 4-octyloxydiphenyliodonium hexafluorophosphate, bis (4-tert-butylbenzene) iodonium hexafluoroantimonate, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3, 4-dimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) - (4-methoxyphenyl) -acetonitrile, (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) -o-methylphenyl-acetonitrile, (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) -phenylacetonitrile.
23. The photoresist composition according to any one of claims 2 to 7, where the surfactant is one or more selected from the group consisting of: anionic surfactants, cationic surfactants, nonionic surfactants, and zwitterionic surfactants.
24. The photoresist composition according to any one of claims 1 to 7, where the photoresist composition comprises the following parts by weight of the components:
(A)10-50 parts of a polymer of formula (I);
(B)1-20 parts of a photoinitiator;
(C)20-85 parts of a solvent;
(D)0.1-10 parts of n-butylamine; and
(E)0.1-10 parts of surfactant.
25. The photoresist composition according to claim 24, wherein the photoresist composition comprises the following components in parts by weight:
(A)15-45 parts of a polymer of formula (I);
(B)2-10 parts of a photoinitiator;
(C)25-80 parts of a solvent;
(D)0.5-5 parts of n-butylamine; and
(E)0.1-5 parts of surfactant.
26. The photoresist composition according to claim 24, wherein the photoresist composition comprises the following components in parts by weight:
(A)25-40 of a polymer of formula (I);
(B)3-8 parts of a photoinitiator;
(C)30-70 parts of a solvent;
(D)0.8-3 parts of n-butylamine; and
(E)0.1-1 parts of surfactant.
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| PCT/CN2018/122325 WO2019134528A1 (en) | 2018-01-05 | 2018-12-20 | Photoresist composite using poly (p-hydroxystyrene)-containing epoxy resin as film-forming resin |
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Denomination of invention: Photoresist composition comprising poly-p-hydroxystyrene epoxy resin as film-forming resin Effective date of registration: 20211210 Granted publication date: 20201211 Pledgee: China Construction Bank Jingmen jinlongquan sub branch Pledgor: HUBEI GURUN TECHNOLOGY Co.,Ltd. Registration number: Y2021420000138 |