WO2018205818A1 - 聚对羟基苯乙烯类环氧树脂、其合成及应用 - Google Patents

聚对羟基苯乙烯类环氧树脂、其合成及应用 Download PDF

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WO2018205818A1
WO2018205818A1 PCT/CN2018/083911 CN2018083911W WO2018205818A1 WO 2018205818 A1 WO2018205818 A1 WO 2018205818A1 CN 2018083911 W CN2018083911 W CN 2018083911W WO 2018205818 A1 WO2018205818 A1 WO 2018205818A1
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formula
polymer
photoresist
film
group
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PCT/CN2018/083911
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English (en)
French (fr)
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邹应全
郭晔嘉
王政
庞玉莲
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湖北固润科技股份有限公司
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Priority to US16/612,962 priority Critical patent/US20200199273A1/en
Priority to EP18798327.5A priority patent/EP3636678B1/en
Priority to KR1020197036489A priority patent/KR102657940B1/ko
Priority to JP2020513388A priority patent/JP7350719B2/ja
Publication of WO2018205818A1 publication Critical patent/WO2018205818A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C08F212/24—Phenols or alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F112/22—Oxygen
    • C08F112/24—Phenols or alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/08—Epoxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • 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
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

Definitions

  • This invention relates to poly(p-hydroxystyrene) epoxy resins.
  • This resin can be used as a film-forming resin for a photoresist system.
  • the invention also relates to the preparation of poly(p-hydroxystyrene) epoxy resins and their use as film-forming resins in photoresist systems.
  • the photoresist is an etch-resistant film material whose solubility changes under irradiation or irradiation of a light source such as an ultraviolet light, an excimer laser, an electron beam, an ion beam, or an X-ray. Since its invention in the 1950s, photoresist has become the core process material in the semiconductor industry and is widely used in the manufacture of integrated circuits and printed circuit boards. In the early 1990s, photoresist was applied to the processing of LCD devices, which played an important role in promoting the large size, high definition and colorization of LCD panels. Photoresist also plays a pivotal role in the fine processing of microelectronics manufacturing from micron, submicron, deep submicron to nanoscale.
  • solubility of the photoresist before and after exposure it can be divided into a positive photoresist and a negative photoresist.
  • the solubility of the positive photoresist increases after exposure and development, and the solubility of the negative photoresist decreases after exposure and development.
  • positive photoresists have the advantages of high resolution, strong resistance to dry etching, good heat resistance, easy gel removal, good contrast, etc., but poor adhesion and mechanical strength, and high cost.
  • the negative photoresist has good adhesion to the substrate, acid and alkali resistance, and fast speed. However, due to cross-linking in the exposed area, the solubility is weakened, which causes deformation and swelling during development, thereby limiting its Resolution.
  • Lithography has gone from g-line (436 nm) lithography, i-line (365 nm) lithography, to KrF (deep ultraviolet 248 nm) lithography, ArF (deep ultraviolet 193 nm) lithography, and next-generation extreme ultraviolet (EUV, 13.5).
  • Nm The development of lithography, corresponding to the photoresist of each exposure wavelength also came into being.
  • the key formulation components in the photoresist such as film-forming resins, photoinitiators, and additives, also change, making the overall performance of the photoresist better meet the process requirements.
  • Micro-Electro-Mechanical System is a miniaturized mechatronics intelligent system consisting of three main components: micro-sensor, micro-actuator and micro-energy.
  • the system size is generally micron or even smaller, and the internal structure size is even micron. nanoscale.
  • Micro-electromechanical systems have the advantages of miniaturization, intelligence, integration, multi-function and suitable for mass production. They have broad development prospects in the fields of military, aerospace, information and communication, biomedicine, automatic control, and automobile industry.
  • MEMS fabrication is achieved by a photolithography process. Unlike the pursuit of higher resolution in lithography processes in general integrated circuit fabrication, MEMS fabrication pursues higher aspect ratios, which require photoresists for MEMS to have a certain thickness. In order to meet the needs of the development of MEMS products, thick film photoresist came into being. In general, thick film photoresists require good photosensitivity and aspect ratio, and coating thicknesses typically range to at least 10 microns.
  • thick glue can be directly used as a working part of MEMS devices, or as a sacrificial layer material to fabricate MEMS devices with film structures and cantilever structures, or as a mask layer for wet etching, or as an electroplated Model for making 3D MEMS devices with non-silicon materials. Therefore, with the continuous development of MEMS, it is very important to develop thick film photoresist suitable for MEMS manufacturing.
  • the commercially available thick film lithography positive adhesives mainly include AZ series positive glue, SJR3000 series positive glue, Ma-p100 positive glue and SPR 220-7 positive glue, etc.
  • the negative glue is negative by SU-8 series produced by American MicroChem Company. Glue-based.
  • diazonaphthoquinone positive photoresists mainly composed of phenolic resin, photosensitive compound diazonaphthoquinone and organic solvent.
  • the diazonaphthoquinone compound in the exposed area undergoes photolysis reaction, loses a molecule of nitrogen, and the Wolff rearrangement is converted into hydrazine carboxylic acid, so that the film can be dissolved in the alkaline developing solution.
  • SU-8 series photoresist is an epoxy resin photoresist. Due to its good chemical, optical and mechanical properties, it has become the most widely used and widely used lithographic thick adhesive in MEMS.
  • the main components of the SU-8 photoresist include a bisphenol A type novolac epoxy resin, an organic solvent ( ⁇ -butyrolactone or cyclopentanone), and a small amount of a photoacid generator triarylsulfonium salt. When exposed, the triarylsulfonium salt absorbs photons and releases a strong acid.
  • the epoxy group in the acid-catalyzed epoxy resin undergoes cationic polymerization cross-linking, and the cross-linking reaction grows in chains, which can be formed quickly.
  • the photoacid generator cannot produce acid, and thus cannot catalyze the polymerization and crosslinking of the epoxy group, and the resin is soluble in the developer during development.
  • the sensitization principle of the SU-8 series photoresist is based on cationic photocuring of epoxy resin.
  • Cationic photocuring system is rapidly developing as an important system in UV curing technology. Compared with free radical photocuring system, its most significant advantage is that it is not inhibited by oxygen, the volume shrinkage rate is small, the curing reaction is not easy to terminate, and the light stops. After that, the curing reaction can continue and the toxicity is low. Due to these advantages, cationic photocurable materials are very suitable for use as a major component of thick film photoresists.
  • cationic photocuring systems mainly include vinyl ether systems, epoxy systems, and oxetane systems.
  • the main advantage of the vinyl ether cationic photocuring system is that the curing rate is very fast, there is no induction period, it can be cured at normal temperature, but there are disadvantages such as poor stability, and the viscosity is low, and it is difficult to form a thick film.
  • the oxetane photocuring system is a relatively new type of cationic photocuring system, which can be cured at room temperature, has low curing shrinkage, and has complete curing, high bonding strength, lower viscosity than epoxy monomers, and curing.
  • the process has an induction period, requires a large amount of exposure, and currently has a small number of monomers and is relatively expensive.
  • Epoxy system is the most commonly used cationic photocuring system. It has a wide variety of monomers, low price, good adhesion after curing, high strength and high viscosity. Although curing is affected by environmental temperature and humidity, the curing reaction rate is slow. However, it can be reduced by appropriate process conditions, and is more suitable for thick film photoresist film-forming resins.
  • an epoxy system mainly including novolac epoxy resin, its main performance characteristics are as described for the film-forming resin of SU-8 photoresist described above, which has the disadvantage that the phenolic resin is synthesized by polycondensation reaction.
  • the degree of polycondensation reaction is not easy to control, and the obtained product has a wide molecular weight distribution, and the product needs to be classified and screened, the process flow is complicated, the operation is difficult, and the cost is high. If the molecular weight of the resin is not uniform, the dissolution in the developer is not uniform, which may affect the resolution of the photoresist.
  • Another type of film-forming resin for photoresist is poly-p-hydroxystyrene and its derivatives.
  • the most widely used is poly-p-hydroxystyrene whose hydroxyl group is protected in whole or in part.
  • the group commonly used as a protecting group has a special group.
  • This type of photoresist is a positive photoresist.
  • the imaging principle is: in the exposed area, the acid generated by the acid generator catalyzes the decomposition of the film-forming resin, removes the protective group, and dissolves in the alkaline developer instead of the exposed area.
  • the resin is insoluble in the alkaline developer due to the presence of the protecting group.
  • the imaging principle of the poly-p-hydroxystyrene-based lithographic negative adhesive is: in the exposed region, the acid-catalyzed crosslinking agent reacts with the film-forming resin to cause the exposed resin to be insoluble in the developer, and the non-exposed area is dissolved in the developer. .
  • the obtained photoresist is not a thick film photoresist, and is a common photoresist.
  • the inventors of the present invention conducted extensive and intensive research on the film-forming resin of photoresist, in order to find a new film-forming resin for cationic photocurable photoresist.
  • the film-forming resin has the advantages of good ultraviolet light transmittance, large viscosity to form a thick film, fast photospeed, and high resolution.
  • the present inventors have found that the epoxy resin moiety is introduced on the polyparaxyl styrene molecule, and the resulting modified resin can achieve the aforementioned object.
  • polypara-hydroxystyrene is used as the main structure, and polyparaxyl styrene itself is synthesized by polyaddition reaction, and a resin having a high molecular weight and a narrow molecular weight distribution can be obtained by a cation-controlled living polymerization method, and a poly-p-hydroxy group is obtained.
  • Styrene has good UV light transmission, and high molecular weight, narrow molecular weight distribution, good UV light transmission and other characteristics are beneficial to improve the resolution of the photoresist; a large amount of benzene ring, benzene exists in the resin structure
  • the rigidity of the ring makes the resin have good etching resistance; the epoxy group is introduced into the resin, the epoxy group can undergo cationic photopolymerization, the photospeed is fast, and there is no oxygen inhibition, so the polymerization reaction is not easy to terminate, in the dark.
  • the modified resin has a good application prospect in the field of thick film photoresist.
  • the present invention has been achieved based on the foregoing findings.
  • the resin When used as a film-forming resin for a photoresist, the resin has the advantages of good ultraviolet light transmittance, high viscosity to form a thick film, fast photospeed, and high resolution.
  • Another object of the present invention is to provide a process for preparing a modified polypara-hydroxystyrene resin containing an epoxy moiety of the present invention.
  • Still another object of the present invention is the use of the modified polypara-hydroxystyrene resin containing an epoxy moiety of the present invention as a film-forming resin in a photoresist.
  • Still another object of the present invention is a photoresist comprising the modified polypara-hydroxystyrene resin containing an epoxy moiety of the present invention.
  • Each of R a -R d , each of R a0 -R d0 , each of R a1 -R d1 and each of R a2 -R d2 are each independently selected from H, halogen, C 1- C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, C 3 -C 12 cycloalkyl and halo C 3 a group of -C 12 cycloalkyl;
  • n and n 0 are each independently a number from 0 to 40, and n + n 0 is a number from 20 to 40;
  • n 1 and n 2 are each independently a number from 0 to 5.
  • each of R a - R d , each of R a0 - R d0 , each of R a1 - R d1 and each of R a2 - R d2 Each independently is selected from the group consisting of H, chlorine, bromine, C 1 -C 4 alkyl, chloro C 1 -C 4 alkyl, bromo C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chlorine a group of a C 1 -C 4 alkoxy group and a bromo C 1 -C 4 alkoxy group; preferably R a -R d , R a0 -R d0 , R a1 -R d1 and R a2 -R d2 are both H.
  • n and n 0 are each independently usually a number from 0 to 40, preferably a number from 0 to 20, more preferably a number from 12 to 18, and n + n 0 is
  • the number of 20-40 is preferably a number of 24-36, more preferably a number of 25-30.
  • n 1 and n 2 are each independently a number from 0 to 5, preferably a number from 0 to 2, more preferably 0; and/or n 1 +n 2 is a number from 0 to 5, preferably a number from 0 to 3, and more preferably 0.
  • n' n+n 0 +n 1 +n 2
  • R a -R d , n, n 0 , n 1 and n 2 are each as defined in any one of items 1 to 4, and X is a halogen, It is preferably chlorine or bromine.
  • a photoresist comprising the polymer of the formula (I) according to any one of items 1 to 4 as a film-forming resin.
  • the photoresist according to item 12 wherein the photoacid generator is any one or more of an iodonium salt, a sulfonium salt, and a heterocyclic acid generator; preferably the iodonium salt is produced.
  • the acid agent, the sulfonium salt acid generator and the heterocyclic acid generator have the following general formulae (IV), (V) and (VI):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently phenyl, halophenyl, nitrophenyl, C 6 -C 10 aryl or C a 1- C 10 alkyl substituted benzoyl;
  • Y, Z are non-nucleophilic anions such as triflate, BF 4 - , ClO 4 - , PF 6 - , AsF 6 - or SbF 6 - .
  • the photopolymerizable monomer is N-vinylpyrrolidone, hydroxyethyl methacrylate or a mixture thereof; and/or
  • the basic additive is a tertiary amine and/or a quaternary amine, more preferably any one or more of triethanolamine, trioctylamine and tributylamine; and/or
  • the sensitizer is any one or more of 2,4-diethylthiaxanthone, 9-fluorenyl methanol and 1-[(2,4-dimethylphenyl)azo]-2-naphthol Kind; and/or
  • the photoresist solvent is any one or more of cyclopentanone, ⁇ -butyrolactone, and ethyl acetate.
  • Example 1 is a lithographic image of four photoresists obtained in Example 9;
  • Example 2 is a lithographic image of four photoresists obtained in Example 10.
  • Each of R a -R d , each of R a0 -R d0 , each of R a1 -R d1 and each of R a2 -R d2 are each independently selected from H, halogen, C 1- C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, C 3 -C 12 cycloalkyl and halo C 3 a group of -C 12 cycloalkyl;
  • n and n 0 are each independently a number from 0 to 40, but n + n 0 is a number from 20 to 40;
  • n 1 and n 2 are each independently a number from 0 to 5.
  • R a -R d , R a0 -R d0 , R a1 -R d1 and R a2 -R d2 are a group on the benzene ring.
  • R a -R d are the same or different from each other
  • R a0 - R d0 are the same or different from each other
  • R a1 - R d1 are the same or different from each other
  • R a2 - R d2 are the same or different from each other, and are each independently selected from H, Halogen, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkoxy, C 3 -C 12 cycloalkyl and halogen a group of a C 3 -C 12 cycloalkyl group.
  • each of R a -R d , each of R a0 -R d0 , each of R a1 -R d1 and each of R a2 -R d2 are each independently selected from H , chlorine, bromine, C 1 -C 4 alkyl, chloro C 1 -C 4 alkyl, bromo C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chloro C 1 -C 4 alkane a group of an oxy group and a brominated C 1 -C 4 alkoxy group.
  • R a -R d , R a0 -R d0 , R a1 -R d1 and R a2 -R d2 are both H.
  • R a , R a0 , R a1 and R a2 may be the same or different, and are preferably the same.
  • R b , R b0 , R b1 and R b2 may be the same or different, preferably the same.
  • R c , R c0 , R c1 and R c2 may be the same or different, preferably the same.
  • R d , R d0 , R d1 and R d2 may be the same or different, preferably the same.
  • n, n 0 , n 1 and n 2 each independently represent the number of structural units of the polypara-hydroxystyrene epoxy resin.
  • n and n 0 are each independently usually a number from 0 to 40, preferably a number from 0 to 20, more preferably a number from 12 to 18.
  • n+n 0 is usually a number of 20-40, preferably a number of 24-36, more preferably a number of 25-30.
  • n 1 and n 2 are each independently a number from 0 to 5, preferably a number from 0 to 2, and more preferably 0.
  • n 1 + n 2 is usually a number from 0 to 5, preferably a number from 0 to 3, and more preferably 0.
  • n' n+n 0 +n 1 +n 2
  • R a -R d , n, n 0 , n 1 and n 2 are each as defined for the polymer of formula (I)
  • X is a halogen, preferably Chlorine or bromine.
  • 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.
  • a basic catalyst is one or more of NaOH, KOH, Na 2 CO 3 , K 2 CO 3 . It is particularly preferred that the basic catalyst is K 2 CO 3 .
  • the reaction of the polymer of the formula (II) with the compound of the formula (III) is not particularly limited with respect to the amount of the basic catalyst.
  • the polymer of formula (II) and the basic catalyst are used in an amount such that the molar ratio of monomer units to basic catalyst contained in the polymer of formula (II) 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 an amount such that the molar ratio of monomer units to basic catalyst contained in the polymer of formula (II) is from 1:0.6 to 1:1.
  • the reaction of the polymer of formula (II) with the compound of formula (III) generally ensures that the polymer of formula (II) is sufficiently reactive.
  • the polymer of formula (II) and the compound of formula (III) are used in an amount such that the molar ratio of monomer units contained in the polymer of formula (II) to the compound of formula (III) is generally from 1:1 to 1:3.
  • the polymer of formula (II) and the compound of formula (III) are used in an amount such that the molar ratio of monomer units of formula (II) to compound of formula (III) is from 1:1.8 to 1:2.0.
  • the reaction of the polymer of the formula (II) with the compound of the formula (III) is usually carried out in a solution.
  • the solvent is one or more selected from the group consisting of ethanol, acetone, ethyl acetate, dichloromethane, and chloroform. It is particularly preferred that the organic solvent is one selected from the group consisting of ethanol and acetone.
  • the reaction of the polymer of the formula (II) with the compound of the formula (III) is conventional for the reaction conditions such as temperature and pressure.
  • the reaction is carried out at 0-30 °C. It is especially preferred that the reaction be carried out at 25-30 °C.
  • the reaction time is advantageously from 8 to 10 hours.
  • the reaction pressure is advantageously atmospheric.
  • Step 1) mixing the polymer of formula (II) and a basic catalyst in a solvent to obtain a mixture;
  • Step 2) slowly adding a compound of the formula (III) to the mixture obtained in the step 1) to carry out a reaction;
  • Step 3) After the reaction is completed, it is filtered, and the solvent and excess reactant are distilled off under reduced pressure to give a solid, which is washed, filtered, and dried to give a polymer of formula (I).
  • the operation of the step 1) can be carried out by first adding a polymer of the formula (II), stirring, introducing nitrogen gas, and then adding a basic catalyst to obtain a mixture.
  • the operation of the step 2) can be carried out by slowly dropwise adding the compound of the formula (III) at 25 to 30 ° C in the mixture obtained in the step 1), and carrying out the reaction for 8 to 10 hours.
  • step 3 The operation of the step 3) can be carried out after the reaction is completed, the undissolved basic catalyst and the produced inorganic salt are removed by filtration, the filtrate is distilled under reduced pressure, and the solvent and excess compound of the formula (III) are distilled off to obtain a solid, washed with water and filtered. After drying, the polymer of formula (I) is obtained.
  • a polymer of the formula (I) according to the invention as a film-forming resin in a photoresist.
  • polypara-hydroxystyrene is used as a main structure, and polypara-hydroxystyrene itself is synthesized by addition polymerization, and can be controlled by a cation.
  • the living polymerization method obtains a resin having a high molecular weight and a narrow molecular weight distribution, and the poly-p-hydroxystyrene has excellent ultraviolet light transmittance, and the high molecular weight, narrow molecular weight distribution, and good ultraviolet light transmittance are all characterized. It is beneficial to improve the resolution of the photoresist; a large number of benzene rings exist in the resin structure, and the rigidity of the benzene ring makes the resin have good etching resistance; the epoxy group is introduced into the resin, and the epoxy group can undergo cationic photopolymerization.
  • the photospeed is fast, there is no oxygen inhibition, so the polymerization reaction is not easy to terminate, and the polymerization can be continued in the dark, and a crosslinked network is easily formed in the exposed area, thereby obtaining a high-resolution lithographic pattern; another advantage of the epoxy resin The viscosity is large, so that the obtained film has good adhesion on the substrate, and a thick photoresist film can be obtained.
  • a photoresist comprising the polymer of formula (I) of the invention as a film-forming resin.
  • the photoresist of the present invention consists essentially of the following components: a polymer of formula (I) as a film-forming resin, a photoacid generator, a photopolymerizable monomer, a basic additive, a sensitizer, and light.
  • Glue solvent Preferably, the mass ratio of the film-forming resin, photoacid generator, photopolymerizable monomer, basic additive, sensitizer, and photoresist solvent is (30-40):(1-4): (20-25): (1-2): (0-2): (40-50).
  • the mass ratio of the film-forming resin, photoacid generator, photopolymerizable monomer, basic additive, sensitizer and photoresist solvent is 35:3.0:25:1.5:1.5:50 .
  • substantially herein is meant that at least 90% by weight, more preferably at least 95% by weight, especially at least 98% by weight, in particular at least 99% by weight, of the total weight of the photoresist is from the formula (I) as a film-forming resin.
  • the photoresist film-forming resin is any one or more of the polymers of the formula (I).
  • the photoacid generator is any one or more of an iodonium salt, a sulfonium salt and a heterocyclic acid generator.
  • the iodonium salt acid generator, the sulfonium salt acid generator and the heterocyclic acid generator have the following general formulae (IV), (V) and (VI):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently phenyl, halophenyl, nitrophenyl, C 6 -C 10 aryl or C 1 -C 10 alkyl substituted benzoyl;
  • Y, Z are non-nucleophilic anions such as triflate, BF 4 - , ClO 4 - , PF 6 - , AsF 6 - or SbF 6 - .
  • the photopolymerizable monomer is N-vinylpyrrolidone, hydroxyethyl methacrylate or a mixture thereof.
  • the basic additive is a tertiary amine and/or a quaternary amine, more preferably any one or more of triethanolamine, trioctylamine and tributylamine.
  • the sensitizer is a sensitizer sensitive to a specific wavelength, such as 2,4-diethylthiazinone, 9-oxime methanol and 1-[(2,4-xylene) Any one or more of azo]-2-naphthol.
  • the photoresist solvent is any one or more of cyclopentanone, ⁇ -butyrolactone and ethyl acetate.
  • the beneficial effect of the polymer of the formula (I) of the invention as a film-forming resin of a photoresist is that the resin has a poly(p-hydroxystyrene) as a main structure, and the poly-p-hydroxystyrene itself is synthesized by a polyaddition reaction, and can be synthesized by a cation.
  • the method of controlled living polymerization obtains a resin having a high molecular weight and a narrow molecular weight distribution; and the poly(p-hydroxystyrene) has good ultraviolet light transmittance, and high molecular weight, narrow molecular weight distribution, and good ultraviolet light transmittance are favorable. Improve the resolution of the photoresist.
  • an epoxy group is introduced into the film-forming resin of the present invention, and the epoxy group can undergo cationic photopolymerization and photosensitivity.
  • the speed is fast, there is no oxygen inhibition, so the polymerization reaction is not easy to terminate, and the polymerization can be continued in the dark, and a crosslinked network is easily formed in the exposed area, thereby obtaining a high-resolution lithographic pattern; another advantage of the epoxy resin is viscosity. Large, so adhesion on the substrate is good, and a thicker photoresist film can be obtained.
  • the infrared spectrum was measured by Shimadzu IRAffinity Fourier Transform Infrared Spectrometer, the scanning range was 4000-400 cm -1 , and the samples were processed by KBr tableting.
  • the sample was formulated into a solution having a concentration of 30 ppm using acetonitrile as a solvent, and the ultraviolet absorption spectrum was measured by a Shimadzu UV-2450 ultraviolet-visible spectrophotometer.
  • the measurement range was 200-400 nm, the resolution was 0.1 nm, and the band width was 0.1-5 nm. , stray light is 0.015% or less.
  • the epoxy value of the sample was measured by the hydrochloric acid-acetone method. Accurately weigh about 0.4g of sample, add it to a 250mL closed conical flask, add 25mL 0.2mol / L hydrochloric acid acetone solution, shake to make the sample completely dissolved, after standing at room temperature for 2h, add 3 drops of phenolphthalein reagent, The solution was titrated with a 0.1 mol/L sodium hydroxide-ethanol standard solution until the solution turned pink, and two blank titrations were carried out under the same conditions. Record the volume of the sodium hydroxide standard solution required for titration, and calculate the epoxy value of the sample according to the formula (1).
  • the nuclear magnetic data are as follows (d-CDCl 3 ): methylene at ⁇ 1.87 polystyrene chain; methylene at ⁇ 2.50 epoxy ring; methine at ⁇ 2.76 polystyrene chain; ⁇ 6.69, 7.02 H on the phenyl ring; methylene group attached to the oxygen in the ⁇ 4.07 epoxy propoxy group; methine group in the ⁇ 3.04 epoxy ring, no hydroxyl group signal detected.
  • Ultraviolet absorption spectrum results: the maximum absorption wavelength is 226 nm, there is no ultraviolet absorption peak above 226 nm, and there is good light transmission in the ultraviolet light region above 226 nm.
  • Epoxy value measurement result The epoxy value was 0.57 mol/100 g.
  • the nuclear magnetic data are as follows (d-CDCl 3 ): methylene at ⁇ 1.87 polystyrene chain; ⁇ 2.34 methyl; ⁇ 2.50 epoxy methylene; ⁇ 2.76 polymethyl methine ⁇ 6.63 H on the benzene ring; methylene group attached to oxygen in ⁇ 4.07 epoxy propoxy group; methine group in ⁇ 3.04 epoxy ring, no hydroxyl signal detected.
  • Ultraviolet absorption spectroscopy results the maximum absorption wavelength is 219 nm, there is no ultraviolet absorption peak above 219 nm, and there is good light transmission in the ultraviolet region above 219 nm.
  • Epoxy value measurement result The epoxy value was 0.49 mol/100 g.
  • the nuclear magnetic data are as follows (d-CDCl3): methylene at ⁇ 1.87 polystyrene chain; ⁇ 1.33 methyl; ⁇ 3.98 ethoxymethylene methylene; ⁇ 2.50 epoxy ring methylene; ⁇ 2 .76 methine in the polystyrene chain; ⁇ 6.58, H on the 6.53 benzene ring; methylene group attached to the oxygen in the ⁇ 4.07 epoxy propoxy group; methine methyl group in the ⁇ 3.04 epoxy ring; No hydroxyl signal was detected.
  • Ultraviolet absorption spectroscopy results the maximum absorption wavelength is 223 nm, there is no ultraviolet absorption peak above 223 nm, and there is good light transmission in the ultraviolet light region above 223 nm.
  • Epoxy value measurement result The epoxy value was 0.45 mol/100 g.
  • the nuclear magnetic data are as follows (d-CDCl3): methylene at ⁇ 1.87 polystyrene chain; methine in ⁇ 2.76 polystyrene chain; ⁇ 6.57, 6.70, 6.96 on benzene ring; ⁇ 4.07 ring a methylene group attached to oxygen in an oxypropoxy group; a methine group in a ⁇ 3.04 epoxy ring; a methylene group in a ⁇ 2.50 epoxy ring, and no hydroxyl group signal detected.
  • Ultraviolet absorption spectroscopy results the maximum absorption wavelength is 217 nm, there is no ultraviolet absorption peak above 217 nm, and there is good light transmission in the ultraviolet region above 217 nm.
  • Epoxy value measurement result The epoxy value was 0.47 mol/100 g.
  • the nuclear magnetic data are as follows (d-CDCl3): methylene group in ⁇ 1.87 polystyrene chain; methine group in ⁇ 2.76 polystyrene chain; ⁇ 6.70, H on 7.02 benzene ring; ⁇ 4.07 epoxide a methylene group attached to oxygen in an oxy group; a methine group in a ⁇ 3.04 epoxy ring; a ⁇ 4.64 chloromethyl group; a methylene group in a ⁇ 2.50 epoxy ring; a weak hydroxyl group detected at ⁇ 5.07 .
  • Ultraviolet absorption spectroscopy results the maximum absorption wavelength is 224 nm, there is no ultraviolet absorption peak above 224 nm, and there is good light transmission in the ultraviolet region above 224 nm.
  • Epoxy value measurement result The epoxy value was 0.40 mol/100 g.
  • the nuclear magnetic data are as follows (d-CDCl3): methylene at ⁇ 1.87 polystyrene chain; methine in ⁇ 2.76 polystyrene chain; ⁇ 6.38, H on 6.41 benzene ring; ⁇ 4.07 epoxide a methylene group attached to oxygen in an oxy group; a methine group in a ⁇ 3.04 epoxy ring; a ⁇ 2.35 methyl group; a ⁇ 3.73 methoxy group; a ⁇ 2.50 epoxy methylene group, ⁇ 5.03 A weak hydroxyl peak was detected.
  • Ultraviolet absorption spectroscopy results the maximum absorption wavelength is 218 nm, there is no ultraviolet absorption peak above 218 nm, and there is good light transmission in the ultraviolet light region above 218 nm.
  • Epoxy value measurement result The epoxy value was 0.40 mol/100 g.
  • the nuclear magnetic data are as follows (d-CDCl3): methylene at ⁇ 1.87 polystyrene chain; methine in ⁇ 2.76 polystyrene chain; ⁇ 6.89, 6.84, 6.61 on the benzene ring; ⁇ 4.07 ring Methylene group attached to oxygen in oxypropoxy group; methine group in ⁇ 3.04 epoxy ring; methylene group in ⁇ 2.50 epoxy ring, ⁇ 1.51 cyclopropyl methine group; ⁇ 0.51 ring A propylene methylene group; a small hydroxyl peak was detected at ⁇ 5.41.
  • Ultraviolet absorption spectrum results: the maximum absorption wavelength is 226 nm, there is no ultraviolet absorption peak above 226 nm, and there is good light transmission in the ultraviolet light region above 226 nm.
  • Epoxy value measurement result The epoxy value was 0.42 mol/100 g.
  • the nuclear magnetic data are as follows (d-CDCl 3 ): methylene at ⁇ 1.87 polystyrene chain; methine in ⁇ 2.76 polystyrene chain; ⁇ 6.47, H on 6.59 benzene ring; ⁇ 4.07 epoxy Methylene group attached to oxygen in propoxy group; methine group in ⁇ 3.04 epoxy ring; methylene group in ⁇ 2.50 epoxy ring, methyl group in ⁇ 1.33 ethoxy group; ⁇ 3.98 ethoxy group Methylene; a weak hydroxyl peak was detected at ⁇ 5.13.
  • Ultraviolet absorption spectroscopy results the maximum absorption wavelength is 220 nm, there is no ultraviolet absorption peak above 220 nm, and there is good light transmission in the ultraviolet region above 220 nm.
  • Epoxy value measurement result The epoxy value was 0.37 mol/100 g.
  • photoresists were prepared as follows: 30 g of each of the polymers prepared in Examples 1-4, 2 g of 3-nitrophenyl. diphenylthio hexafluorophosphate, 25 g of N were prepared. -vinylpyrrolidone, 1.8 g of trioctylamine, 1 g of 9-oxime methanol and 50 g of ethyl acetate, the above materials are mixed and thoroughly stirred to completely dissolve, and filtered through a 0.45 ⁇ m polytetrafluoroethylene microporous membrane to obtain Four new negative chemical amplification photoresists.
  • photoresists were prepared as follows: 40 g of each of the polymers prepared in Examples 5-8, 3 g of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 20 g of hydroxyethyl methacrylate, 1.5 g of triethanolamine, 1.5 g of 2,4-diethylthiaxanone and 50 g of cyclopentanone, the above materials were mixed and thoroughly stirred to completely dissolve, and passed through 0.45 ⁇ m of polytetrafluoroethylene.
  • Four kinds of new negative chemical amplification photoresists can be obtained by filtering the ethylene microporous membrane.
  • the four negative chemically amplified photoresists obtained in the above Example 9 were respectively coated on a 6-inch single crystal silicon wafer by spin coating (rotation speed: 4000 rpm), baked at 90 ° C for 2 minutes, and cooled to room temperature, and then coated.
  • a good silicon wafer was exposed to an exposure machine having a wavelength of 365 nm, and after baking, it was baked at 110 ° C for 2 minutes, and developed with a propylene glycol methyl ether acetate aqueous solution as a developing solution for 60 s to obtain a lithographic image.
  • the lithographic images of the photoresists obtained in the polymers obtained in Examples 1-4 are shown in Figures 1(a)-(d), respectively.
  • the four negative chemically amplified photoresists obtained in the above Example 10 were respectively coated on a 6-inch single crystal silicon wafer by spin coating (rotation speed: 4000 rpm), baked at 100 ° C for 2 minutes, and cooled to room temperature, and then coated.
  • a good silicon wafer was exposed to an exposure machine having a wavelength of 248 nm, and after baking, it was baked at 100 ° C for 2 minutes, and developed with a propylene glycol methyl ether acetate aqueous solution as a developing solution for 50 s to obtain a lithographic image.
  • the lithographic images of the photoresists obtained in Examples 5-8 were as shown in Figures 2(a)-(d), respectively.
  • Fig. 1 the polymer obtained in the examples 1-4 is used as a film-forming resin, and the obtained photoresist is prepared, and after exposure, development and the like, a clear pattern with a diameter of about 30 ⁇ m can be obtained, and the resolution is high.
  • the graphics are arranged neatly, the edges are complete, and there is no glue or residue.
  • the polymer obtained in the examples 5-8 is used as a film-forming resin to prepare a photoresist. After exposure, development, etc., the obtained film is thick, and the sidewall of the pattern is steep and high. Up to 70 ⁇ m, aspect ratio up to 1:1.
  • the polymer prepared in the above examples is used for a negative chemically amplified photoresist, based on cationic photocuring of epoxy groups, using a chemical amplification technique, with a polyhydroxystyrene structure as its main component, its high molecular weight, The narrow molecular weight distribution and good UV light transmission make the photoresist have good resolution.
  • the introduction of the epoxy structure makes the resin easily form a crosslinked network in the exposed area, thereby obtaining a high-resolution lithographic pattern; in addition, the viscosity of the epoxy resin is large, so that the obtained adhesive film has good adhesion on the substrate and is easily obtained.
  • the thicker photoresist film after exposure and development, can obtain a clear pattern with a diameter of 30 ⁇ m, and the film thickness can reach 70 ⁇ m, which has a good application prospect in the field of thick film photoresist.

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Abstract

本发明涉及一种式(I)的聚合物，其中Ra-Rd、Ra0-Rd0、Ra1-Rd1、Ra2-Rd2、n、n0、n1和n2如说明书中所定义。该聚合物当用作光刻胶的成膜树脂时具有紫外光透过性好、粘度大可形成厚膜、感光速度快、分辨率高等优点。本发明还涉及制备式(I)聚合物的方法，式(I)聚合物在光刻胶中作为成膜树脂的用途，以及包含式(I)聚合物作为成膜树脂的光刻胶。

Description

聚对羟基苯乙烯类环氧树脂、其合成及应用 技术领域
本发明涉及聚对羟基苯乙烯类环氧树脂。该树脂可用作光刻胶体系的成膜树脂。本发明还涉及聚对羟基苯乙烯类环氧树脂的制备以及它们在光刻胶体系中作为成膜树脂的应用。
背景技术
光刻胶是在紫外光、准分子激光、电子束、离子束、X射线等光源的照射或辐射下，溶解度发生变化的耐蚀刻薄膜材料。自二十世纪五十年代被发明以来，光刻胶就成为半导体行业最核心的工艺材料，广泛应用于集成电路和印制电路板的制造中。二十世纪九十年代初，光刻胶又被运用到LCD器件的加工制作，对LCD面板的大尺寸化、高精细化、彩色化起到了重要的推动作用。在微电子制造业精细加工从微米级、亚微米级、深亚微米级进入到纳米级水平的过程中，光刻胶也起到了举足轻重的关键性作用。
根据光刻胶在曝光前后溶解度的变化情况，可分为正性光刻胶和负性光刻胶。正性光刻胶经曝光和显影后溶解度增加，负性光刻胶经曝光和显影后溶解度减小。一般来说，正性光刻胶具有高分辨率、抗干法刻蚀性强、耐热性好、去胶方便、对比度好等优点，但粘附性和机械强度较差，且成本较高。而负性光刻胶对基材有良好的粘附能力、耐酸耐碱、感光速度快，但由于在曝光区域发生交联，溶解能力减弱，导致显影时容易变形和溶胀，从而限制了它的分辨率。
随着电子器件不断向高集成化和精细化发展，对光刻胶分辨率等性能的要求也不断提高。光刻技术经历了从g线(436nm)光刻，i线(365nm)光刻，到KrF(深紫外248nm)光刻，ArF(深紫外193nm)光刻，以及下一代极紫外(EUV，13.5nm)光刻的发展历程，相对应于各曝光波长的光刻胶也应运而生。光刻胶中的关键配方成分，如成膜树脂、光引发剂、添加剂也随之发生变化，使光刻胶的综合性能更好地满足工艺要求。
微机电系统(MEMS)是一个微型化的机械电子智能系统，由微传感器、微执 行器和微能源三个主要部分组成，其系统尺寸一般在微米级甚至更小，内部结构尺寸在微米级甚至纳米级。微机电系统具有微型化、智能化、集成化、多功能以及适于批量生产等优点，在军事、航空航天、信息通信、生物医学、自动控制、汽车工业等领域都有广阔的发展前景。
MEMS器件的微结构制造是通过光刻工艺来实现的。与一般集成电路制造中光刻工艺追求更高分辨率不同，MEMS制造追求的是更高的深宽比，这就要求用于MEMS的光刻胶具有一定的厚度。为了满足MEMS产品发展的需要，厚膜光刻胶应运而生。一般来说，厚膜光刻胶需要有良好的光敏性和深宽比，涂层厚度通常至少达到10微米。在MEMS制造中，厚胶可直接作为MEMS器件的工作部件，也可以作为牺牲层材料来制作膜结构和悬臂梁结构的MEMS器件，或者作为湿法刻蚀的掩膜层，还可作为电镀的模型，用于制作非硅材料的三维MEMS器件。因此，随着MEMS的不断发展，开发出适于MEMS制造的厚膜光刻胶十分重要。
目前已商品化的厚膜光刻正胶主要有AZ系列正胶、SJR3000系列正胶、Ma-p100正胶以及SPR 220-7正胶等，负胶以美国MicroChem公司生产的SU-8系列负胶为主。
商品化的正性厚膜光刻胶大都属于重氮萘醌正性光刻胶，主要由酚醛树脂、感光化合物重氮萘醌及有机溶剂组成。在紫外光照射下，曝光区的重氮萘醌化合物发生光解反应，失去一分子氮，发生Wolff重排转变为茚羧酸，使胶膜能溶于碱性显影液。而在非曝光区，光化学反应不能发生，且酚醛树脂的羟基与重氮萘醌化合物通过氢键作用，形成稳定的六元环结构，抑制树脂的溶解。
SU-8系列光刻胶是一种环氧树脂光刻胶，由于具有良好的化学性能、光学性能和力学性能，已成为目前在MEMS领域应用最广泛、最普遍的光刻厚胶。SU-8光刻胶主要成分包括双酚A型酚醛环氧树脂、有机溶剂(γ-丁内酯或环戊酮)以及少量光产酸剂三芳基硫鎓盐。曝光时，三芳基硫鎓盐吸收光子，释放出强酸，在后烘过程中，酸催化环氧树脂中的环氧基团发生阳离子聚合交联，交联反应以链式增长，能够很快形成大分子量的致密交联网络结构，这种网络结构在显影过程中不溶于显影液，从而保留下来。而在非曝光区，光产酸剂不能产酸，也就无法催化环氧基团聚合交联，在显影过程中树脂可溶于显影液。
SU-8系列光刻胶的感光原理是基于环氧树脂的阳离子光固化。阳离子光固化体系作为UV固化技术中的重要体系正在迅速发展，与自由基光固化体系相比，它最显著的优点就是不被氧阻聚，固化体积收缩率小，固化反应不易终止，光照停止后，固化反应仍能继续进行，且毒性较低。由于具备这些优点，阳离子光固化材料十分适用于作为厚膜光刻胶的主要成分。
目前，阳离子光固化体系主要有乙烯基醚体系、环氧体系和氧杂环丁烷体系。
乙烯基醚阳离子光固化体系的主要优点有固化速率非常快，没有诱导期，在常温下即可固化，但存在稳定性差等缺点，且粘度较低，不易形成厚膜。
氧杂环丁烷光固化体系是一种较为新型的阳离子光固化体系，常温下即可固化，固化收缩率低，且固化较彻底，粘接强度高，粘度比环氧类单体低，固化过程存在诱导期，需要较大的曝光量，且目前单体种类较少，价格较贵。
环氧体系是目前最常用的阳离子光固化体系，其单体种类丰富，价格低廉，固化后黏附性好，强度高，粘度高，虽然固化受环境温度、湿度影响大，固化反应速率较慢，但可以通过适当的工艺条件减小其影响，较适用于厚膜光刻胶成膜树脂。作为环氧体系，主要包括酚醛环氧树脂，它的主要性能特点就是如对前面介绍的SU-8光刻胶的成膜树脂所述，它存在的缺点：酚醛树脂是通过缩聚反应合成而来，缩聚反应程度不易控制，得到的产物分子量分布较宽，需要对产物进行分级筛选，工艺流程复杂且不易操作、成本较高。如果树脂分子量不均匀，在显影液中的溶解就不均匀，会影响光刻胶的分辨率。
另一类光刻胶用成膜树脂是聚对羟基苯乙烯及其衍生物，其中应用最广泛的是羟基被全部或部分保护的聚对羟基苯乙烯，常用作保护基的基团有特丁基碳酸酯、缩醛、缩酮、硅烷基等。这一类光刻胶是正性光刻胶，其成像原理是：在曝光区，产酸剂产生的酸催化成膜树脂分解，脱去保护基团，溶于碱性显影液，而非曝光区的树脂由于保护基团的存在，不能溶于碱性显影液。聚对羟基苯乙烯类光刻负胶的成像原理是：在曝光区，酸催化交联剂与成膜树脂发生交联反应，使曝光区树脂不溶于显影液，而非曝光区溶于显影液。然而，目前开发出的聚对羟基苯乙烯类光刻负胶种类较少，而且得到的光刻胶不是厚膜光刻胶，是普通光刻胶。
发明内容
鉴于现有技术中存在的问题，本发明的发明人在光刻胶的成膜树脂方面进行了广泛而又深入的研究，以期发现一种新的阳离子光固化型光刻胶用成膜树脂，该成膜树脂具有紫外光透过性好、粘度大可形成厚膜、感光速度快、分辨率高等优点。本发明人发现，在聚对羟基苯乙烯分子上引入环氧结构部分，所得改性树脂可以实现前述目的。其中，以聚对羟基苯乙烯作为主体结构，聚对羟基苯乙烯本身是通过加聚反应而合成的，可用阳离子可控活性聚合的方法得到具有高分子量和窄分子量分布的树脂，且聚对羟基苯乙烯有很好的紫外光透过性，而高分子量、窄分子量分布、良好的紫外光透过性等特点都有利于提高光刻胶的分辨率；树脂结构中存在大量的苯环，苯环的刚性使树脂具有良好的抗刻蚀能力；树脂中引入了环氧基团，环氧基团可以发生阳离子光聚合，感光速度快，没有氧阻聚，因此聚合反应不易终止，在暗处也可以继续聚合，在曝光区容易形成交联网络，从而得到高分辨率的光刻图形；环氧树脂的另一个优点是粘度大，因此所得胶膜在基底上黏附性好，而且可以得到较厚的光刻胶膜。由于具备这些优点，所述改性树脂在厚膜光刻胶领域具有良好的应用前景。本发明正是基于前述发现得以实现。
因此，本发明的一个目的是提供一种含有环氧结构部分的改性聚对羟基苯乙烯树脂。该树脂当用作光刻胶的成膜树脂时具有紫外光透过性好、粘度大可形成厚膜、感光速度快、分辨率高等优点。
本发明的另一个目的是提供一种制备本发明的含有环氧结构部分的改性聚对羟基苯乙烯树脂的方法。
本发明的再一个目的是本发明的含有环氧结构部分的改性聚对羟基苯乙烯树脂在光刻胶中作为成膜树脂的用途。
本发明的又一个目的是包含本发明的含有环氧结构部分的改性聚对羟基苯乙烯树脂的光刻胶。
实现本发明上述目的的技术方案可以概括如下：
1.下式(I)聚合物：
Figure PCTCN2018083911-appb-000001
其中：
R a-R d中的每一个、R a0-R d0中的每一个、R a1-R d1中的每一个和R a2-R d2中的每一个各自独立地为选自H、卤素、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 3-C 12环烷基和卤代C 3-C 12环烷基的基团；
n和n 0各自独立地为0-40的数，n+n 0为20-40的数；以及
n 1和n 2各自独立地为0-5的数。
2.根据第1项的聚合物，其中R a-R d中的每一个、R a0-R d0中的每一个、R a1-R d1中的每一个和R a2-R d2中的每一个各自独立地为选自H、氯、溴、C 1-C 4烷基、氯代C 1-C 4烷基、溴代C 1-C 4烷基、C 1-C 4烷氧基、氯代C 1-C 4烷氧基和溴代C 1-C 4烷氧基的基团；优选R a-R d、R a0-R d0、R a1-R d1和R a2-R d2均为H。
3.根据第1或2项的化合物，其中n和n 0各自独立地通常为0-40的数，优选为0-20的数，更优选为12-18的数，并且n+n 0为20-40的数，优选为24-36的数，更优选为25-30的数。
4.根据第1-3项中任一项的聚合物，其中n 1和n 2各自独立地为0-5的数，优选为0-2的数，更优选为0；和/或n 1+n 2为0-5的数，优选为0-3的数，更优选为0。
5.一种制备根据第1-4项中任一项的式(I)聚合物的方法，包括使式(II)聚合物与式(III)化合物进行反应，
Figure PCTCN2018083911-appb-000002
其中n’＝n+n 0+n 1+n 2，R a-R d、n、n 0、n 1和n 2各自如第1-4项中任一项所定义，以及X为卤素，优选为氯或溴。
6.根据第5项的方法，其中式(II)聚合物与式(III)化合物的反应在碱性催化剂存在下进行，优选碱性催化剂为选自NaOH、KOH、Na 2CO 3、K 2CO 3中的一种或多种，更优选为K 2CO 3。
7.根据第5或6项的方法，其中式(II)聚合物和式(III)化合物的用量应使得式(II)聚合物所含单体单元与式(IH)化合物的摩尔比为1∶1-1∶3，优选为1∶1.8-1∶2.0。
8.根据第5-7项中任一项的方法，其中式(II)聚合物和碱性催化剂的用量应使得式(II)聚合物所含单体单元与碱性催化剂的摩尔比为1∶0.1-1∶1，优选为1∶0.6-1∶1。
9.根据第5-8项中任一项的方法，其中式(II)聚合物与式(HI)化合物的反应在0-30℃下进行，优选在25-30℃下进行。
10.根据第1-4项中任一项的式(I)聚合物在光刻胶中作为成膜树脂的用途。
11.一种包含根据第1-4项中任一项的式(I)聚合物作为成膜树脂的光刻胶。
12.根据第11项的光刻胶，其包含作为成膜树脂的根据第1-4项中任一项的式(I)聚合物、光致产酸剂、光聚合单体、碱性添加剂、敏化剂和光刻胶溶剂；优选所述成膜树脂、光致产酸剂、光聚合单体、碱性添加剂、敏化剂和光刻胶溶剂的质量配比是(30-40)∶(1-4)∶(20-25)∶(1-2)∶(0-2)∶(40-50)；更优选所述成膜树脂、光致产酸剂、光聚合单体、碱性添加剂、敏化剂和光刻胶溶剂的质量配比是35∶3.0∶25∶1.5∶1.5∶50。
13.根据第12项的光刻胶，其中所述光致产酸剂为碘鎓盐、硫鎓盐和杂环类产酸剂中的任一种或几种；优选所述碘鎓盐产酸剂、硫鎓盐产酸剂和杂环类 产酸剂分别具有如下通式(IV)、(V)和(VI)：
Figure PCTCN2018083911-appb-000003
其中R 1、R 2、R 3、R 4、R 5、R 6、R 7和R 8各自独立地是苯基、卤代苯基、硝代苯基、C 6-C 10芳基或C 1-C 10烷基取代的苯甲酰基；以及
Y、Z是非亲核性阴离子，例如三氟甲磺酸根、BF 4 -、ClO 4 -、PF 6 -、AsF 6 -或者SbF 6 -。
14.根据第12或13项的光刻胶，其中
所述光聚合单体为N-乙烯基吡咯烷酮、甲基丙烯酸羟乙酯或其混合物；和/或
所述碱性添加剂为叔胺类和/或季胺类物质，更优选三乙醇胺、三辛胺和三丁胺中的任一种或几种；和/或
所述敏化剂为2，4-二乙基硫杂蒽酮、9-蒽甲醇和1-[(2，4-二甲苯基)偶氮]-2-萘酚中的任一种或几种；和/或
所述光刻胶溶剂为环戊酮、γ-丁内酯和乙酸乙酯中的任一种或几种。
本发明的这些和其它目的、特征和优点在结合下文考虑本发明后，将易于为普通技术人员所明白。
附图说明
图1是实施例9所得四种光刻胶的光刻图像；以及
图2是实施例10所得四种光刻胶的光刻图像。
具体实施方式
根据本发明的一个方面，提供了一种下式(I)的聚合物：
Figure PCTCN2018083911-appb-000004
其中：
R a-R d中的每一个、R a0-R d0中的每一个、R a1-R d1中的每一个和R a2-R d2中的每一个各自独立地为选自H、卤素、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 3-C 12环烷基和卤代C 3-C 12环烷基的基团；
n和n 0各自独立地为0-40的数，但n+n 0为20-40的数；以及
n 1和n 2各自独立地为0-5的数。
在本发明中，R a-R d、R a0-R d0、R a1-R d1和R a2-R d2为苯环上的基团。R a-R d彼此相同或不同，R a0-R d0彼此相同或不同，R a1-R d1彼此相同或不同，以及R a2-R d2彼此相同或不同，并且各自独立地为选自H、卤素、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 3-C 12环烷基和卤代C 3-C 12环烷基的基团。优选的是，R a-R d中的每一个、R a0-R d0中的每一个、R a1-R d1中的每一个和R a2-R d2中的每一个各自独立地为选自H、氯、溴、C 1-C 4烷基、氯代C 1-C 4烷基、溴代C 1-C 4烷基、C 1-C 4烷氧基、氯代C 1-C 4烷氧基和溴代C 1-C 4烷氧基的基团。特别优选的是，R a-R d、R a0-R d0、R a1-R d1和R a2-R d2均为H。另外，R a、R a0、R a1和R a2可以相同或不同，优选相同。R b、R b0、R b1和R b2可以相同或不同，优选相同。R c、R c0、R c1和R c2可以相同或不同，优选相同。R d、R d0、R d1和R d2可以相同或不同，优选相同。
在本发明中，n、n 0、n 1和n 2各自独立地表示聚对羟基苯乙烯环氧树脂的结构单元的数量。n和n 0各自独立地通常为0-40的数，优选为0-20的数，更优选为12-18的数。n+n 0通常为20-40的数，优选为24-36的数，更优选为25-30的数。n 1和n 2各自独立地为0-5的数，优选为0-2的数，更优选为0。n 1+n 2通常 为0-5的数，优选为0-3的数，更优选为0。
根据本发明的另一个方面，还提供了一种制备本发明式(I)聚合物的方法，包括使式(II)聚合物与式(III)化合物进行反应，
Figure PCTCN2018083911-appb-000005
其中n’＝n+n 0+n 1+n 2，R a-R d、n、n 0、n 1和n 2各自如对式(I)聚合物所定义，以及X为卤素，优选为氯或溴。
本发明中，式(II)聚合物与式(III)化合物的反应通常在碱性催化剂存在下进行。对于碱性催化剂的选择没有特别的限制。优选的是，碱性催化剂为NaOH、KOH、Na 2CO 3、K 2CO 3中的一种或多种。特别优选的是，碱性催化剂为K 2CO 3。本发明中，式(II)聚合物与式(III)化合物的反应对于碱性催化剂的用量没有特别的限制。优选的是，式(II)聚合物和碱性催化剂的用量应使得式(II)聚合物所含单体单元与碱性催化剂的摩尔比为1∶0.1-1∶1。特别优选的是，式(II)聚合物和碱性催化剂的用量应使得式(II)聚合物所含单体单元与碱性催化剂的摩尔比为1∶0.6-1∶1。
本发明中，式(II)聚合物与式(III)化合物的反应通常要保证式(II)聚合物反应充分。因此，式(II)聚合物和式(III)化合物的用量应使得式(II)聚合物所含单体单元与式(III)化合物的摩尔比通常为1∶1-1∶3。优选的是，式(II)聚合物和式(III)化合物的用量应使得式(II)聚合物所含单体单元与式(III)化合物的摩尔比为1∶1.8-1∶2.0。
本发明中，式(II)聚合物与式(III)化合物的反应通常在溶液中进行。对于溶剂的选择没有特别的限制，只要能溶解各反应物即可。有利的是，式(II)聚合物与式(III)化合物的反应在有机溶剂存在下进行。优选的是，有机溶剂为选自乙醇、丙酮、乙酸乙酯、二氯甲烷、三氯甲烷中的一种或多种。特别优选的是，有机溶剂为选自乙醇和丙酮中的一种。
本发明中，式(II)聚合物与式(III)化合物的反应对于温度压力等反应条件的要求是常规的。优选的是，反应在0-30℃下进行。特别优选的是，反应在25-30℃下进行。反应时间有利地为8-10小时。反应压力有利地为常压。
通过对制备得到的产物进行红外表征，观察红外谱图中3500cm -1附近处反应前后羟基锋是否减弱甚至消失或环氧基的引入来判断是否得到了本发明的式(I)聚合物，并通过 1H-NMR确定产物结构。
作为举例，通过式(II)聚合物与式(III)化合物的反应来制备式(I)聚合物通常可按照如下所述来进行：
步骤1)：在溶剂中，将式(II)聚合物和碱性催化剂混合，得到混合物；
步骤2)：在步骤1)得到的混合物中缓慢滴加式(III)化合物，进行反应；以及
步骤3)：反应完成后，过滤，减压蒸馏除去溶剂和过量的反应物，得到固体后，洗涤、过滤、干燥，得到式(I)聚合物。
步骤1)的操作可以这样进行：在溶剂中，先加入式(II)聚合物，搅拌，通入氮气，再加入碱性催化剂，得到混合物。
步骤2)的操作可以这样进行：在步骤1)中得到的混合物中于25-30℃下缓慢滴加式(III)化合物，并进行反应8-10小时。
步骤3)的操作可以这样进行：反应完成后，过滤除去未溶解的碱性催化剂和生成的无机盐，滤液减压蒸馏，蒸掉溶剂和过量的式(III)化合物，得到固体，水洗、过滤、干燥后，得到式(I)聚合物。
根据本发明的再一个方面，提供了本发明式(I)聚合物在光刻胶中作为成膜树脂的用途。当本发明的式(I)聚合物用作光刻胶的成膜树脂时，以聚对羟基苯乙烯作为主体结构，聚对羟基苯乙烯本身是通过加聚反应而合成的，可用阳离子可控活性聚合的方法得到具有高分子量和窄分子量分布的树脂，且聚对羟基苯乙烯有很好的紫外光透过性，而高分子量、窄分子量分布、良好的紫外光透过性等特点都有利于提高光刻胶的分辨率；树脂结构中存在大量的苯环，苯环的刚性使树脂具有良好的抗刻蚀能力；树脂中引入了环氧基团，环氧基团可以发生阳离子光聚合，感光速度快，没有氧阻聚，因此聚合反应不易终止，在暗处也可以继续聚合，在曝光区容易形成交联网络，从而得到高分辨率的光刻图 形；环氧树脂的另一个优点是粘度大，因此所得胶膜在基底上黏附性好，而且可以得到较厚的光刻胶膜。
根据本发明的最后一个方面，提供了包含本发明式(I)聚合物作为成膜树脂的光刻胶。
通常而言，本发明的光刻胶基本上由以下组分组成：作为成膜树脂的式(I)聚合物、光致产酸剂、光聚合单体、碱性添加剂、敏化剂和光刻胶溶剂。优选的是，所述成膜树脂、光致产酸剂、光聚合单体、碱性添加剂、敏化剂和光刻胶溶剂的质量配比是(30-40)∶(1-4)∶(20-25)∶(1-2)∶(0-2)∶(40-50)。更优选的是，所述成膜树脂、光致产酸剂、光聚合单体、碱性添加剂、敏化剂和光刻胶溶剂的质量配比是35∶3.0∶25∶1.5∶1.5∶50。这里的“基本上”指的是，光刻胶总重量的至少90重量％，更优选至少95重量％，尤其是至少98重量％，特别是至少99重量％由作为成膜树脂的式(I)聚合物、光致产酸剂、光聚合单体、碱性添加剂、敏化剂和光刻胶溶剂组成。
本发明中，所述光刻胶成膜树脂为式(I)聚合物中任一种或几种。
根据本发明优选的是，所述光致产酸剂为碘鎓盐、硫鎓盐和杂环类产酸剂中的任一种或几种。有利的是，所述碘鎓盐产酸剂、硫鎓盐产酸剂和杂环类产酸剂的分别具有如下通式(IV)、(V)和(VI)：
Figure PCTCN2018083911-appb-000006
其中
R 1、R 2、R 3、R 4、R 5、R 6、R 7和R 8各自独立地是苯基、卤代苯基、硝代苯基、C 6-C 10芳基或C 1-C 10烷基取代的苯甲酰基；以及
Y、Z是非亲核性阴离子，例如三氟甲磺酸根、BF 4 -、ClO 4 -、PF 6 -、AsF 6 -或者SbF 6 -。
根据本发明优选的是，所述光聚合单体为N-乙烯基吡咯烷酮、甲基丙烯酸羟乙酯或其混合物。
根据本发明优选的是，所述碱性添加剂为叔胺类和/或季胺类物质，更优选的是三乙醇胺、三辛胺和三丁胺中的任一种或几种。
根据本发明优选的是，所述敏化剂为对特定波长敏感的敏化剂，如2，4-二乙基硫杂蒽酮、9-蒽甲醇和1-[(2，4-二甲苯基)偶氮]-2-萘酚中的任一种或几种。
根据本发明优选的是，所述光刻胶溶剂为环戊酮、γ-丁内酯和乙酸乙酯中的任一种或几种。
本发明的式(I)聚合物作为光刻胶的成膜树脂的有益效果是：树脂以聚对羟基苯乙烯作为主体结构，聚对羟基苯乙烯本身通过加聚反应而合成，可通过阳离子可控活性聚合的方法得到具有高分子量和窄分子量分布的树脂；且聚对羟基苯乙烯有很好的紫外光透过性，而高分子量、窄分子量分布、良好的紫外光透过性都有利于提高光刻胶的分辨率。树脂结构中存在大量的苯环，苯环的刚性使树脂具有良好的抗刻蚀能力。尤其特别的是，与其他以聚对羟基苯乙烯作为主体的光刻胶成膜树脂相比，本发明的成膜树脂中引入了环氧基团，环氧基团可以发生阳离子光聚合，感光速度快，没有氧阻聚，因此聚合反应不易终止，在暗处也可以继续聚合，在曝光区容易形成交联网络，从而得到高分辨率的光刻图形；环氧树脂的另一个优点是粘度大，因此在基底上黏附性好，而且可以得到较厚的光刻胶膜。
实施例
以下将结合具体实施例对本发明作进一步说明，但不应将其理解为对本发明保护范围的限制。
下述实施例中涉及的表征和检测方法如下：
1.红外光谱表征方法
红外光谱用岛津公司IRAffinity傅里叶变换红外光谱仪测定，扫描范围4000-400cm -1，样品用KBr压片法处理。
2. 1H NMR谱表征方法
1H NMR用Bruker Avame PRX400核磁共振仪测定，化学位移以ppm表示，溶剂为氘代氯仿，内标为四甲基硅烷，扫描宽度400MHz，扫描次数16次。
3.紫外吸收光谱测定方法
以乙腈为溶剂，将样品配制成浓度为30ppm的溶液，用岛津公司UV-2450紫外可见分光光度计测定紫外吸收光谱，测定波长范围200-400nm，分辨率0.1nm，谱带宽度0.1-5nm，杂散光0.015％以下。
4.环氧值测定方法
采用盐酸-丙酮法测定试样的环氧值。准确称取约0.4g的样品，加入到250mL密闭锥形瓶中，加入25mL 0.2mol/L的盐酸丙酮溶液，摇匀使样品完全溶解，在室温下静置2h后，加入3滴酚酞试剂，用0.1mol/L的氢氧化钠-乙醇标准溶液滴定至溶液变为粉色，按相同条件进行两次空白滴定。记录滴定所需氢氧化钠标准溶液的体积，按计算式(1)计算试样的环氧值。
Figure PCTCN2018083911-appb-000007
式中：
E-环氧值，mol/100g；
V 1-空白实验消耗的氢氧化钠-乙醇标准溶液的体积，mL；
V 2-试样消耗的氢氧化钠-乙醇标准溶液的体积，mL；
c NaOH-氢氧化钠-乙醇标准溶液的浓度，mol/L；
m-试样的质量，g。
实施例1：聚4-(2’，3’-环氧丙氧基)苯乙烯
取50ml丙酮为溶剂，向溶剂中加入12g聚对羟基苯乙烯(数均分子量3000，n’＝25)(0.1mol重复单元)，电动搅拌，通入氮气，加入氢氧化钠2.4g(0.06mol)。将所得反应混合物的温度控制在25℃，通过恒压滴液漏斗缓慢滴加16.65g环氧氯丙烷(0.18mol)，0.5h内滴加完毕，之后使所得反应混合物于25℃下反应8h。反应完成后，过滤掉未溶的无机物，滤液减压蒸馏，蒸去溶剂和过量的环氧氯丙烷，得到固体，用水洗涤三次，过滤，干燥得产物，经分析为标题聚合物。
核磁数据如下(d-CDCl 3)：δ1.87聚苯乙烯链中亚甲基；δ2.50环氧环中亚甲基；δ2.76聚苯乙烯链中次甲基；δ6.69，7.02苯环上的H；δ4.07环氧丙氧基中与氧相连的亚甲基；δ3.04环氧环中次甲基，未检测到羟基信号。
红外光谱结果：3100cm -1-3500cm -1处未检测到羟基伸缩振动峰，910cm -1处检测到环氧环的特征吸收峰。
紫外吸收光谱结果：最大吸收波长226nm，在226nm以上无紫外吸收峰，在226nm以上紫外光区有很好的光透过性。
环氧值测定结果：环氧值为0.57mol/100g。
实施例2：聚3，5-二甲基-4-(2’，3’-环氧丙氧基)苯乙烯
取50ml乙醇为溶剂，向溶剂中加入14.8g聚3，5-二甲基-4-羟基苯乙烯(数均分子量2960，n’＝20)(0.1mol重复单元)，电动搅拌，通入氮气，加入氢氧化钾5.6g(0.1mol)。将所得反应混合物的温度控制在20℃，通过恒压滴液漏斗缓慢滴加18.5g环氧氯丙烷(0.2mol)，0.5h内滴加完毕，之后使所得反应混合物于25℃下反应8h。反应完成后，过滤掉未溶的无机物，滤液减压蒸馏，蒸去溶剂和过量的环氧氯丙烷，得到固体，用水洗涤三次，过滤，干燥得产物，经分析为标题聚合物。
核磁数据如下(d-CDCl 3)：δ1.87聚苯乙烯链中亚甲基；δ2.34甲基；δ2.50环氧环中亚甲基；δ2.76聚苯乙烯链中次甲基；δ6.63苯环上的H；δ4.07环氧丙氧基中与氧相连的亚甲基；δ3.04环氧环中次甲基，未检测到羟基信号。
红外光谱结果：3100cm -1-3500cm -1处未检测到羟基伸缩振动峰，911cm -1处检测到环氧环的特征吸收峰。
紫外吸收光谱结果：最大吸收波长219nm，在219nm以上无紫外吸收峰，在219nm以上紫外光区有很好的光透过性。
环氧值测定结果：环氧值为0.49mol/100g。
实施例3：聚3-乙氧基-4-(2’，3’-环氧丙氧基)苯乙烯
取50ml乙酸乙酯为溶剂，向溶剂中加入16.4g聚3-乙氧基-4-羟基苯乙烯(数均分子量4920，n＝30)(0.1mol重复单元)，电动搅拌，通入氮气，加入碳酸钾8.28g(0.06mol)。将所得反应混合物的温度控制在30℃，通过恒压滴液漏斗缓慢滴加18.5g环氧氯丙烷(0.2mol)，0.5h内滴加完毕，之后使所得反应混合物于25℃下反应10h。反应完成后，过滤掉未溶的无机物，滤液减压蒸馏，蒸去溶剂和 过量的环氧氯丙烷，得到固体，用水洗涤三次，过滤，干燥得产物，经分析为标题聚合物。
核磁数据如下(d-CDCl3)：δ1.87聚苯乙烯链中亚甲基；δ1.33甲基；δ3.98乙氧基中亚甲基；δ2.50环氧环中亚甲基；δ2.76聚苯乙烯链中次甲基；δ6.58，6.53苯环上的H；δ4.07环氧丙氧基中与氧相连的亚甲基；δ3.04环氧环中次甲基；未检测到羟基信号。
红外光谱结果：3100cm -1-3500cm -1处未检测到羟基伸缩振动峰，914cm -1处检测到环氧环的特征吸收峰。
紫外吸收光谱结果：最大吸收波长223nm，在223nm以上无紫外吸收峰，在223nm以上紫外光区有很好的光透过性。
环氧值测定结果：环氧值为0.45mol/100g。
实施例4：聚2-氯-4-(2’，3’-环氧丙氧基)苯乙烯
取50ml乙酸乙酯为溶剂，向溶剂中加入15.5g聚2-氯-4-羟基苯乙烯(数均分子量3887，n＝25)(0.1mol重复单元)，电动搅拌，通入氮气，加入碳酸钠6.36g(0.06mol)。将所得反应混合物的温度控制在30℃，通过恒压滴液漏斗缓慢滴加16.65g环氧氯丙烷(0.18mol)，0.5h内滴加完毕，之后使所得反应混合物于30℃下反应9h。反应完成后，过滤掉未溶的无机物，滤液减压蒸馏，蒸去溶剂和过量的环氧氯丙烷，得到固体，用水洗涤三次，过滤，干燥得产物，经分析为标题聚合物。
核磁数据如下(d-CDCl3)：δ1.87聚苯乙烯链中亚甲基；δ2.76聚苯乙烯链中次甲基；δ6.57，6.70，6.96苯环上的H；δ4.07环氧丙氧基中与氧相连的亚甲基；δ3.04环氧环中次甲基；δ2.50环氧环中亚甲基，未检测到羟基信号。
红外光谱结果：3100cm -1-3500cm -1处未检测到羟基伸缩振动峰，914cm -1处检测到环氧环的特征吸收峰。
紫外吸收光谱结果：最大吸收波长217nm，在217nm以上无紫外吸收峰，在217nm以上紫外光区有很好的光透过性。
环氧值测定结果：环氧值为0.47mol/100g。
实施例5：聚2-氯甲基-4-(2’，3’-环氧丙氧基)苯乙烯
取50ml二氯甲烷为溶剂，向溶剂中加入17g聚2-氯甲基-4-羟基苯乙烯(数均分子量5055，n＝30)(0.1mol重复单元)，电动搅拌，通入氮气，加入氢氧化钠2.4g(0.06mol)。将所得反应混合物的温度控制在30℃，通过恒压滴液漏斗缓慢滴加16.65g环氧氯丙烷(0.18mol)，0.5h内滴加完毕，之后使所得反应混合物于25℃下反应8h。反应完成后，过滤掉未溶的无机物，滤液减压蒸馏，蒸去溶剂和过量的环氧氯丙烷，得到固体，用水洗涤三次，过滤，干燥得产物，经分析为标题聚合物。
核磁数据如下(d-CDCl3)：δ1.87聚苯乙烯链中亚甲基；δ2.76聚苯乙烯链中次甲基；δ6.70，7.02苯环上的H；δ4.07环氧丙氧基中与氧相连的亚甲基；δ3.04环氧环中次甲基；δ4.64氯甲基；δ2.50环氧环中亚甲基；δ5.07处检测到微弱的羟基峰。
红外光谱结果：3100cm -1-3500cm -1处检测到微弱的羟基伸缩振动峰，914cm -1处检测到环氧环的特征吸收峰。
紫外吸收光谱结果：最大吸收波长224nm，在224nm以上无紫外吸收峰，在224nm以上紫外光区有很好的光透过性。
环氧值测定结果：环氧值为0.40mol/100g。
实施例6：聚2-甲基-5-甲氧基-4-(2’，3’-环氧丙氧基)苯乙烯
取50ml丙酮为溶剂，向溶剂中加入16.4g聚2-甲基-5-甲氧基-4-羟基苯乙烯(数均分子量5740，n＝35)(0.1mol重复单元)，电动搅拌，通入氮气，加入碳酸钾11.04g(0.08mol)。将所得反应混合物的温度控制在30℃，通过恒压滴液漏斗缓慢滴加17.58g环氧氯丙烷(0.19mol)，0.5h内滴加完毕，之后使所得反应混合物于25℃下反应8h。反应完成后，过滤掉未溶的无机物，滤液减压蒸馏，蒸去溶剂和过量的环氧氯丙烷，得到固体，用水洗涤三次，过滤，干燥得产物，经分析为标题聚合物。
核磁数据如下(d-CDCl3)：δ1.87聚苯乙烯链中亚甲基；δ2.76聚苯乙烯链中次甲基；δ6.38，6.41苯环上的H；δ4.07环氧丙氧基中与氧相连的亚甲基；δ3.04环氧环中次甲基；δ2.35甲基；δ3.73甲氧基；δ2.50环氧环中亚甲基，δ5.03处 检测到微弱的羟基峰。
红外光谱结果：3100cm -1-3500cm -1处检测到微弱的羟基伸缩振动峰，910cm -1处检测到环氧环的特征吸收峰。
紫外吸收光谱结果：最大吸收波长218nm，在218nm以上无紫外吸收峰，在218nm以上紫外光区有很好的光透过性。
环氧值测定结果：环氧值为0.40mol/100g。
实施例7：聚3-环丙基-4-(2’，3’-环氧丙氧基)苯乙烯
取50ml丙酮为溶剂，向溶剂中加入16.1g聚3-环丙基-4-羟基苯乙烯(数均分子量6440，n＝40)(0.1mol重复单元)，电动搅拌，通入氮气，加入氢氧化钾4.2g(0.075mol)。将所得反应混合物的温度控制在30℃，通过恒压滴液漏斗缓慢滴加17.58g环氧氯丙烷(0.19mol)，0.5h内滴加完毕，之后使所得反应混合物于25℃下反应9h。反应完成后，过滤掉未溶的无机物，滤液减压蒸馏，蒸去溶剂和过量的环氧氯丙烷，得到固体，用水洗涤三次，过滤，干燥得产物，经分析为标题聚合物。
核磁数据如下(d-CDCl3)：δ1.87聚苯乙烯链中亚甲基；δ2.76聚苯乙烯链中次甲基；δ6.89，6.84，6.61苯环上的H；δ4.07环氧丙氧基中与氧相连的亚甲基；δ3.04环氧环中次甲基；δ2.50环氧环中亚甲基，δ1.51环丙基中次甲基；δ0.51环丙基中亚甲基；δ5.41处检测到很小的羟基峰。
红外光谱结果：3100cm -1-3500cm -1处检测到微弱的羟基伸缩振动峰，912cm -1处检测到环氧环的特征吸收峰。
紫外吸收光谱结果：最大吸收波长226nm，在226nm以上无紫外吸收峰，在226nm以上紫外光区有很好的光透过性。
环氧值测定结果：环氧值为0.42mol/100g。
实施例8：聚2-氯-5-乙氧基-4-(2’，3’-环氧丙氧基)苯乙烯
取50ml乙醇为溶剂，向溶剂中加入19.85g聚2-氯-5-乙氧基-4-羟基苯乙烯(数均分子量6948，n＝35)(0.1mol重复单元)，电动搅拌，通入氮气，加入碳酸钠8.48g(0.08mol)。将所得反应混合物的温度控制在30℃，通过恒压滴液漏斗缓 慢滴加18.5g环氧氯丙烷(0.2mol)，0.5h内滴加完毕，之后使所得反应混合物于25℃下反应10h。反应完成后，过滤掉未溶的无机物，滤液减压蒸馏，蒸去溶剂和过量的环氧氯丙烷，得到固体，用水洗涤三次，过滤，干燥得产物，经分析为标题聚合物。
核磁数据如下(d-CDCl 3)：δ1.87聚苯乙烯链中亚甲基；δ2.76聚苯乙烯链中次甲基；δ6.47，6.59苯环上的H；δ4.07环氧丙氧基中与氧相连的亚甲基；δ3.04环氧环中次甲基；δ2.50环氧环中亚甲基，δ1.33乙氧基中甲基；δ3.98乙氧基中亚甲基；δ5.13处检测到微弱的羟基峰。
红外光谱结果：3100cm -1-3500cm -1处检测到微弱的羟基伸缩振动峰，909cm -1处检测到环氧环的特征吸收峰。
紫外吸收光谱结果：最大吸收波长220nm，在220nm以上无紫外吸收峰，在220nm以上紫外光区有很好的光透过性。
环氧值测定结果：环氧值为0.37mol/100g。
实施例9
按照如下所述制备四种负性化学放大光刻胶：分别称取30g实施例1-4各自制得的聚合物、2g 3-硝基苯基.二苯基硫六氟磷酸盐、25g N-乙烯基吡咯烷酮、1.8g三辛胺、1g 9-蒽甲醇和50g乙酸乙酯，将上述物质混合并充分搅拌使之完全溶解，通过0.45μm聚四氟乙烯微孔滤膜过滤，即可得四种新型负性化学放大光刻胶。
实施例10
按照如下所述制备四种负性化学放大光刻胶：分别称取40g实施例5-8各自制得的聚合物、3g双(4-叔丁基苯基)碘三氟甲磺酸盐、20g甲基丙烯酸羟乙酯、1.5g三乙醇胺、1.5g 2，4-二乙基硫杂蒽酮和50g环戊酮，将上述物质混合并充分搅拌使之完全溶解，通过0.45μm聚四氟乙烯微孔滤膜过滤，即可得四种新型负性化学放大光刻胶。
实施例11
将上述实施例9所得四种负性化学放大光刻胶通过旋转涂布(转速4000rpm)分别涂布在6英寸单晶硅片上，在90℃下烘烤2min，冷却至室温后，将涂好的硅片放在波长为365nm的曝光机中曝光，曝光完成后在110℃下烘烤2min，用丙二醇甲醚醋酸酯水溶液作为显影液显影60s，得到光刻图像。实施例1-4所得聚合物制得的光刻胶的光刻图像分别如图1(a)-(d)所示。
实施例12
将上述实施例10所得四种负性化学放大光刻胶通过旋转涂布(转速4000rpm)分别涂布在6英寸单晶硅片上，在100℃下烘烤2min，冷却至室温后，将涂好的硅片放在波长为248nm的曝光机中曝光，曝光完成后在100℃下烘烤2min，用丙二醇甲醚醋酸酯水溶液作为显影液显影50s，得到光刻图像。实施例5-8所得聚合物制得的光刻胶的光刻图像分别如图2(a)-(d)所示。
由图1可见：以实施例1-4制得的聚合物作为成膜树脂，配制得到的光刻胶，经曝光、显影等流程后，可得到直径为约30μm的清晰图形，分辨率高，图形排列规整，边缘完整，无掉胶或残留现象。
由图2可见：以实施例5-8制得的聚合物作为成膜树脂，配制得到的光刻胶，经曝光、显影等流程后，得到的胶膜较厚，图形侧壁陡直，高度可达70μm，深宽比可达1∶1。
上述实施例中制得的聚合物用于负性化学放大光刻胶，以环氧基团的阳离子光固化为基础，采用了化学增幅技术，以聚羟基苯乙烯结构为主体，其高分子量、窄分子量分布、良好的紫外光透过性等特点使光刻胶具有很好的分辨率。环氧结构的引入，使树脂在曝光区容易形成交联网络，从而得到高分辨率的光刻图形；此外，环氧树脂粘度大的特性，使所得胶膜在基底上黏附性好，易得到较厚的光刻胶膜，经曝光、显影后，可得到直径为30μm的清晰图形，膜厚可达70μm，在厚膜光刻胶领域具有良好的应用前景。

Claims (14)

  1. 下式(I)聚合物：
    Figure PCTCN2018083911-appb-100001
    其中：
    R a-R d中的每一个、R a0-R d0中的每一个、R a1-R d1中的每一个和R a2-R d2中的每一个各自独立地为选自H、卤素、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 3-C 12环烷基和卤代C 3-C 12环烷基的基团；
    n和n 0各自独立地为0-40的数，n+n 0为20-40的数；以及
    n 1和n 2各自独立地为0-5的数。
  2. 根据权利要求1的聚合物，其中R a-R d中的每一个、R a0-R d0中的每一个、R a1-R d1中的每一个和R a2-R d2中的每一个各自独立地为选自H、氯、溴、C 1-C 4烷基、氯代C 1-C 4烷基、溴代C 1-C 4烷基、C 1-C 4烷氧基、氯代C 1-C 4烷氧基和溴代C 1-C 4烷氧基的基团；优选R a-R d、R a0-R d0、R a1-R d1和R a2-R d2均为H。
  3. 根据权利要求1或2的化合物，其中n和n 0各自独立地通常为0-40的数，优选为0-20的数，更优选为12-18的数，并且n+n 0为20-40的数，优选为24-36的数，更优选为25-30的数。
  4. 根据权利要求1-3中任一项的聚合物，其中n 1和n 2各自独立地为0-5的数，优选为0-2的数，更优选为0；和/或n 1+n 2为0-5的数，优选为0-3的数，更优选为0。
  5. 一种制备根据权利要求1-4中任一项的式(I)聚合物的方法，包括使式(II) 聚合物与式(III)化合物进行反应，
    Figure PCTCN2018083911-appb-100002
    其中n’＝n+n 0+n 1+n 2，R a-R d、n、n 0、n 1和n 2各自如权利要求1-4中任一项所定义，以及X为卤素，优选为氯或溴。
  6. 根据权利要求5的方法，其中式(II)聚合物与式(III)化合物的反应在碱性催化剂存在下进行，优选碱性催化剂为选自NaOH、KOH、Na 2CO 3、K 2CO 3中的一种或多种，更优选为K 2CO 3。
  7. 根据权利要求5或6的方法，其中式(II)聚合物和式(III)化合物的用量应使得式(II)聚合物所含单体单元与式(III)化合物的摩尔比为1∶1-1∶3，优选为1∶1.8-1∶2.0。
  8. 根据权利要求5-7中任一项的方法，其中式(II)聚合物和碱性催化剂的用量应使得式(II)聚合物所含单体单元与碱性催化剂的摩尔比为1∶0.1-1∶1，优选为1∶0.6-1∶1。
  9. 根据权利要求5-8中任一项的方法，其中式(II)聚合物与式(III)化合物的反应在0-30℃下进行，优选在25-30℃下进行。
  10. 根据权利要求1-4中任一项的式(I)聚合物在光刻胶中作为成膜树脂的用途。
  11. 一种包含根据权利要求1-4中任一项的式(I)聚合物作为成膜树脂的光刻胶。
  12. 根据权利要求11的光刻胶，其包含作为成膜树脂的根据权利要求1-4中任一项的式(I)聚合物、光致产酸剂、光聚合单体、碱性添加剂、敏化剂和光刻胶溶剂；优选所述成膜树脂、光致产酸剂、光聚合单体、碱性添加剂、敏化剂和光刻胶溶剂的质量配比是(30-40)∶(1-4)∶(20-25)∶(1-2)∶(0-2)∶(40-50)；更优选所述成膜树脂、光致产酸剂、光聚合单体、碱性添加剂、敏化剂和光刻胶溶剂的 质量配比是35∶3.0∶25∶1.5∶1.5∶50。
  13. 根据权利要求12的光刻胶，其中所述光致产酸剂为碘鎓盐、硫鎓盐和杂环类产酸剂中的任一种或几种；优选所述碘鎓盐产酸剂、硫鎓盐产酸剂和杂环类产酸剂分别具有如下通式(IV)、(V)和(VI)：
    Figure PCTCN2018083911-appb-100003
    其中R 1、R 2、R 3、R 4、R 5、R 6、R 7和R 8各自独立地是苯基、卤代苯基、硝代苯基、C 6-C 10芳基或C 1-C 10烷基取代的苯甲酰基；以及
    Y、Z是非亲核性阴离子，例如三氟甲磺酸根、BF 4 -、ClO 4 -、PF6 -、AsF 6 -或者SbF 6 -。
  14. 根据权利要求12或13的光刻胶，其中
    所述光聚合单体为N-乙烯基吡咯烷酮、甲基丙烯酸羟乙酯或其混合物；和/或
    所述碱性添加剂为叔胺类和/或季胺类物质，更优选三乙醇胺、三辛胺和三丁胺中的任一种或几种；和/或
    所述敏化剂为2，4-二乙基硫杂蒽酮、9-蒽甲醇和1-[(2，4-二甲苯基)偶氮]-2-萘酚中的任一种或几种；和/或
    所述光刻胶溶剂为环戊酮、γ-丁内酯和乙酸乙酯中的任一种或几种。
PCT/CN2018/083911 2017-05-12 2018-04-20 聚对羟基苯乙烯类环氧树脂、其合成及应用 WO2018205818A1 (zh)

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