CN115542667A - Solvent-free negative photoresist with high resolution and preparation method thereof - Google Patents
Solvent-free negative photoresist with high resolution and preparation method thereof Download PDFInfo
- Publication number
- CN115542667A CN115542667A CN202110723741.2A CN202110723741A CN115542667A CN 115542667 A CN115542667 A CN 115542667A CN 202110723741 A CN202110723741 A CN 202110723741A CN 115542667 A CN115542667 A CN 115542667A
- Authority
- CN
- China
- Prior art keywords
- solvent
- negative photoresist
- epoxy resin
- free negative
- silicone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000003822 epoxy resin Substances 0.000 claims abstract description 22
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 150000003254 radicals Chemical class 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 7
- 125000002091 cationic group Chemical group 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- -1 hexafluorophosphate Chemical compound 0.000 claims description 20
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 11
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 9
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 9
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 9
- GKZPEYIPJQHPNC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GKZPEYIPJQHPNC-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- SEEVRZDUPHZSOX-WPWMEQJKSA-N [(e)-1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(\C)=N\OC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-WPWMEQJKSA-N 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 4
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- CQHKDHVZYZUZMJ-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-prop-2-enoyloxypropyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CO)COC(=O)C=C CQHKDHVZYZUZMJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000011161 development Methods 0.000 claims description 3
- YMCOIFVFCYKISC-UHFFFAOYSA-N ethoxy-[2-(2,4,6-trimethylbenzoyl)phenyl]phosphinic acid Chemical compound CCOP(O)(=O)c1ccccc1C(=O)c1c(C)cc(C)cc1C YMCOIFVFCYKISC-UHFFFAOYSA-N 0.000 claims description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical group C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- OLPZCIDHOZATMA-UHFFFAOYSA-N 2,2-dioxooxathiiran-3-one Chemical class O=C1OS1(=O)=O OLPZCIDHOZATMA-UHFFFAOYSA-N 0.000 claims description 2
- IYAYDWLKTPIEDC-UHFFFAOYSA-N 2-[2-hydroxyethyl(3-triethoxysilylpropyl)amino]ethanol Chemical compound CCO[Si](OCC)(OCC)CCCN(CCO)CCO IYAYDWLKTPIEDC-UHFFFAOYSA-N 0.000 claims description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims description 2
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- IHFRGRYLPFJZGU-UHFFFAOYSA-N CO[SiH](CNc1ccccc1)OC Chemical compound CO[SiH](CNc1ccccc1)OC IHFRGRYLPFJZGU-UHFFFAOYSA-N 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004056 anthraquinones Chemical class 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- KSFBTBXTZDJOHO-UHFFFAOYSA-N diaminosilicon Chemical compound N[Si]N KSFBTBXTZDJOHO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- WCAGGTLUGWSHOV-UHFFFAOYSA-N tris(tert-butylperoxy)-ethenylsilane Chemical compound CC(C)(C)OO[Si](OOC(C)(C)C)(OOC(C)(C)C)C=C WCAGGTLUGWSHOV-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims 3
- 150000003839 salts Chemical class 0.000 claims 2
- GDRWYGWOZQAYRI-UHFFFAOYSA-N 7-(diethylamino)-3-(thiophene-3-carbonyl)chromen-2-one Chemical compound O=C1OC2=CC(N(CC)CC)=CC=C2C=C1C(=O)C=1C=CSC=1 GDRWYGWOZQAYRI-UHFFFAOYSA-N 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 abstract description 16
- 239000010703 silicon Substances 0.000 abstract description 16
- 238000012545 processing Methods 0.000 abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000011521 glass Substances 0.000 abstract 1
- 239000004033 plastic Substances 0.000 abstract 1
- 229920003023 plastic Polymers 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 abstract 1
- 239000003292 glue Substances 0.000 description 32
- 239000000463 material Substances 0.000 description 23
- 238000003848 UV Light-Curing Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 230000006750 UV protection Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 238000010023 transfer printing Methods 0.000 description 2
- CWRBWLKXTXSMEH-UHFFFAOYSA-N 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone Chemical compound C=1C=C2N(CC)C3=CC=C(C(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C CWRBWLKXTXSMEH-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- OCOKYGWIFVEPHU-UHFFFAOYSA-N 3-[diethoxy(3-methylpenta-1,4-dien-3-yloxy)silyl]propane-1,1,1-triamine Chemical compound C(=C)C(C)(O[Si](OCC)(OCC)CCC(N)(N)N)C=C OCOKYGWIFVEPHU-UHFFFAOYSA-N 0.000 description 1
- SEEVRZDUPHZSOX-UHFFFAOYSA-N [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(C)=NOC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-UHFFFAOYSA-N 0.000 description 1
- NRTJGTSOTDBPDE-UHFFFAOYSA-N [dimethyl(methylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[SiH2]O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C NRTJGTSOTDBPDE-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003553 thiiranes Chemical class 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a solvent-free negative photoresist with high resolution and a preparation method thereof, belonging to the field of photoresists. Comprises the following steps: 10-70% of acrylate monomer, 20-80% of organosilicon modified epoxy resin, 0.5-3% of free radical initiator, 1-5% of cationic initiator and 0.5-2% of adhesion promoter. The photoresist is prepared by a two-system compounding mode, and the solvent-free photoresist is environment-friendly; the curing agent has the advantages of high curing speed and high strength, and is suitable for the requirements of rapid laser processing; and has excellent adhesion to substrates such as metal, silicon wafers, glass, plastics and the like; the processing resolution is high, and the method is suitable for processing the micro-nano three-dimensional structure.
Description
Technical Field
The invention relates to the technical field of photocuring materials, in particular to a solvent-free negative photoresist with high resolution.
Background
There are many photo-curable materials, but the photoresist suitable for laser direct writing processing is limited by various factors, usually relying on import, and the photoresist is expensive and has short shelf life, and the shelf life remained after being purchased in a customer is only a few months. To solve this problem, the native supply of photoresist is particularly important.
In order to meet the industrial requirements, the laser direct writing speed is increased increasingly, which also puts higher requirements on the response speed of the material. The purpose of fast response is usually achieved by adopting a glue of a free radical initiation system, but the material of the free radical curing system is difficult to meet the requirements of a three-dimensional structure in the aspects of strength, hardness, adhesive force, shrinkage, refractive index, resolution ratio and the like.
The prior patent publication CN 201611136909.5-a cationic radical hybrid photocuring resin and a preparation method and application thereof, wherein the resin is a common epoxy resin, and the common epoxy resin has poor stability and poor UV resistance, so that the reliability of the material is poor.
The patent publication CN106886128B discloses a negative photoresist, which is characterized in that an episulfide resin is prepared by an alicyclic epoxy monomer and allyl acrylate, and then an anhydride curing agent is used for modifying to obtain a photosensitive resin with high refractive index.
Compared with the prior art, the invention aims to develop an environment-friendly solvent-free negative photoresist material by utilizing the combination of the rapid response speed and the high resolution of a free radical initiation system and the high strength, the excellent adhesive force, the low stress, the low shrinkage and the high reliability of a cation initiation system of organic silicon modified epoxy resin, and the negative photoresist material is mainly used for processing and manufacturing a rapid laser direct-writing micro-nano three-dimensional structure and can also be used for batch transfer printing processing of micro-nano structural members.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the solvent-free negative photoresist with high resolution and the preparation method thereof are provided, the response speed required by rapid laser direct writing can be met, the processed structural member has strong adhesion to a base material, low shrinkage rate and high strength, and a three-dimensional structure can be supported.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a solvent-free type negative photoresist with high resolution comprises the following components in percentage by weight: 10-70% of acrylate monomer, 20-80% of organic silicon modified epoxy resin, 0.5-3% of free radical initiator, 1-5% of cationic initiator and 0.5-2% of adhesion promoter.
The acrylate monomer is one or more of methyl acrylate, ethyl acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol hexaacrylate, urethane acrylate and epoxy acrylate.
Wherein the organic silicon modified epoxy resin is one or more of organic silicon modified alicyclic epoxy resin and organic silicon modified bisphenol A epoxy resin.
Preferably, the epoxy equivalent of the organosilicon modified alicyclic epoxy resin or the organosilicon modified bisphenol A epoxy resin is 180-320g/eq, and the molecular weight of the organosilicon chain segment accounts for 20-60% of the total molecular weight. The epoxy resin modified by organic silicon can improve the overall stability and the UV resistance of the material, thereby improving the reliability of the material in the using process.
Wherein the free radical initiator is one or more of diphenylethanone, alpha-hydroxyalkylphenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, benzoin-bis (methyl ether), benzoin ethyl ether, anthraquinone, thiol, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime), 7-diethylamino-3-thiophenecarboxylcoumarin, and the like.
Wherein the cationic initiator is one or more of aryl diazonium salt, diaryl iodonium salt, triaryl sulfonium salt, alkyl sulfonium salt, iron-aryl complex, cumeneiron hexafluorophosphate, sulfonyloxy ketone and triaryl siloxy ether.
Wherein, the adhesion promoter is organosilicon coupling agent and its modifier, preferably one or more of gamma-methacryloxypropyltrimethoxysilane, diaminosilane, vinyltris (beta-methoxyethoxy) silane, glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, vinyltris- (tert-butylperoxy) silane, divinyltriaminopropyltriethoxysilane, phenylaminomethyldimethoxysilane, N, N-bis- (beta-hydroxyethyl) -gamma-aminopropyltriethoxysilane.
The preparation method of the photoresist comprises the following steps: weighing the metered acrylate monomer, the free radical initiator, the organosilicon modified epoxy resin, the cationic initiator and the adhesion promoter in a lightproof container, and then stirring for 30-120 minutes at the rotating speed of 100-800rpm at the temperature of 40-60 ℃.
When the photoresist is used, after laser exposure and before development, post-baking is needed, the baking temperature is 100-150 ℃, and the baking time is 5-30min.
Preferably, after laser exposure and post-baking, development is carried out with a developer solution, which is suitably acetone or propylene glycol methyl ether acetate, followed by rinsing with isopropanol.
The photoresist is mainly used for processing and manufacturing a micro-nano three-dimensional structure by fast laser direct writing, and can also be used for batch transfer printing processing of micro-nano structural parts.
The invention has the beneficial effects that: compared with the cation curing of common epoxy resin, the cation curing of the epoxy resin modified by organic silicon has the advantages that the obtained polymer material has lower shrinkage and smaller internal stress, so that the adhesion of the prepared three-dimensional structure to a base material is prevented from being reduced due to serious shrinkage, and the material is prevented from being failed in an aging test stage due to cracking, glue explosion and the like caused by large internal stress of epoxy. And the free radical initiation system with high polymerization speed is adopted in combination with the double initiation system to achieve the requirement of high response speed required by processing, so that the processing requirement is met, and the high shrinkage rate of the acrylic acid achieves higher resolution. The strength of the cured material is enhanced by utilizing a cation initiation system to support the processed three-dimensional structure, and the prepared three-dimensional structure has excellent stability due to excellent base material adhesion.
Detailed Description
In order to explain the technical content, the objects achieved, and the effects achieved by the present invention in detail, the following embodiments are specifically described.
In order to highlight the advantages of the present invention, the following comparative examples and examples were compared, wherein the test items and the equipment information used were as follows: laser direct writing equipment, model PPGT2, nano-waxy three-dimensional technology (shanghai) ltd; and (3) testing tensile strength: sheetA column type servo control computer system tensile testing machine, model GT-AI-3000, high-speed rail detection instrument, inc.; and (3) testing the adhesive force: (ii) a hundred grid test method; and (3) microstructure observation: scanning electron microscope, SUPAR40, mercury Carl Zeiss GmbH; and (3) shrinkage rate testing: and (3) filling the size of the metal mold containing the polytetrafluoroethylene coating with the size of 10 x 1mm, and testing the reduction rate of the sizes of the four sides of the molded glue after UV curing, namely the shrinkage rate of the glue. UV light curing machine: model M-25-2x1-URS-TR-SS, company IST METZ GmbH, curing conditions of 800mJ/cm 2 Irradiation time at energy 12s.
The organic silicon modified epoxy resin used in the invention has the following synthetic method:
preparation of organic silicon modified alicyclic epoxy resin
250g of 1, 2-epoxy-4-vinylcyclohexane and 0.10g of chloroplatinic acid olefin chelate complex containing 2% of platinum were placed in a 1000ml three-necked flask equipped with a magnetic stirrer, a thermometer and a constant pressure dropping funnel, and stirred at 200rpm for 5 minutes under nitrogen. The temperature is raised to 70 ℃, 130g of tetramethyldisiloxane is slowly dripped through a constant-pressure dropping funnel, and the addition is finished in 30min. Stirring is continued for 4 hours at 70 ℃, and after cooling to room temperature, the organosilicon modified alicyclic epoxy resin 1 with the epoxy equivalent of about 180g/eq and the molecular weight of the organosilicon chain segment of about 30 percent is obtained.
250g of 1, 2-epoxy-4-vinylcyclohexane and 0.15g of chloroplatinic acid olefin chelate complex containing 2% of platinum were placed in a 1000ml three-necked flask equipped with a magnetic stirrer, a thermometer and a constant pressure dropping funnel, and stirred at 200rpm for 5min under nitrogen. The temperature was raised to 70 ℃ and 280g of octamethyltetrasiloxane were added dropwise slowly through a dropping funnel at constant pressure, and the addition was completed during 60min. Stirring is continued for 4 hours at 70 ℃, and after the temperature is reduced to room temperature, the organosilicon modified alicyclic epoxy resin 2 with the epoxy equivalent of 260g/eq and the organosilicon chain segment molecular weight of about 50 percent is obtained.
250g of 1, 2-epoxy-4-vinylcyclohexane and 0.15g of chloroplatinic acid olefin chelate containing 2% of platinum were charged in a 1000ml three-necked flask equipped with a magnetic stirrer, a thermometer and a dropping funnel with constant pressure, and stirred at 200rpm for 5 minutes with introduction of nitrogen. The temperature is raised to 70 ℃, 430g of dodecamethylhexahydropolysiloxane is slowly dropped through a constant pressure dropping funnel, and 120min is added. Stirring is continued for 4 hours at 70 ℃, and after cooling to room temperature, the organosilicon modified alicyclic epoxy resin 3 with the epoxy equivalent of about 320g/eq and the molecular weight of the organosilicon chain segment of about 60 percent is obtained. Preparation of organic silicon modified bisphenol A epoxy resin
150g of bisphenol A epoxy resin and 300g of benzene solvent are added into a 1000ml four-neck flask provided with a magnetic stirring bar, a thermometer, a condensation tube and a constant pressure dropping funnel, 0.2g of aluminum triacetylacetonate is added, the mixture is heated to 70 ℃, 75g of alpha, w-dihydroxy polydimethylsiloxane is slowly added through the constant pressure dropping funnel, the dropwise addition is completed within 30min, the temperature is raised to 110 ℃, the reaction is carried out for 2 hours, and 200g of toluene is added after the cooling. Then carrying out reduced pressure distillation under the negative pressure of less than 0.5Mpa to obtain the organosilicon modified bisphenol A epoxy resin 1 with the epoxy equivalent of about 180g/eq and the organosilicon chain segment molecular weight of about 20 percent.
150g of bisphenol A epoxy resin and 300g of benzene as a solvent are added into a 1000ml four-neck flask provided with a magnetic stirrer, a thermometer, a condenser tube and a constant pressure dropping funnel, 0.3g of aluminum triacetylacetone is added, the mixture is heated to 70 ℃, 145g of alpha, w-dihydroxy polydimethylsiloxane is slowly added into the mixture through the constant pressure dropping funnel, the dropwise addition is completed within 60min, the temperature is raised to 110 ℃, the reaction is carried out for 2 hours, and 300g of toluene is added after the cooling. Then carrying out reduced pressure distillation under the negative pressure of less than 0.5Mpa to obtain the organosilicon modified bisphenol A epoxy resin 2 with the epoxy equivalent of about 215g/eq and the organosilicon segment molecular weight ratio of about 30 percent.
150g of bisphenol A epoxy resin and 300g of benzene as a solvent are added into a 1000ml four-neck flask provided with a magnetic stirrer, a thermometer, a condenser tube and a constant pressure dropping funnel, 0.4g of aluminum triacetylacetone is added, the mixture is heated to 70 ℃, 364g of alpha, w-dihydroxy polydimethylsiloxane is slowly added into the mixture through the constant pressure dropping funnel, the dropwise addition is completed within 120min, the mixture is heated to 110 ℃ and reacts for 4 hours, and 400g of toluene is added after the mixture is cooled. Then carrying out reduced pressure distillation under the negative pressure of below 0.5Mpa to obtain the organic silicon modified bisphenol A epoxy resin 3 with the epoxy equivalent of about 320g/eq and the molecular weight ratio of an organic silicon chain segment of about 60 percent.
Comparative example 1
The components are as follows: 50 parts of pentaerythritol triacrylate, 47 parts of pentaerythritol hexaacrylate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime) and 2 parts of gamma-methacryloxypropyltrimethoxysilane. These components were stirred at 600rpm for 60 minutes at 60 ℃ to give a gum.
The glue was cured with a UV light curing machine and then tested for relevant mechanical properties and shrinkage.
After the glue is exposed by laser direct writing equipment, post-baking is not needed, excess acetone is directly used for developing for 5min, then isopropanol is used for washing, and then the prepared microstructure is observed by a scanning electron microscope in appearance, resolution, base material bonding condition, shrinkage and the like.
Comparative example No. two
The components are as follows: 20 parts by weight of pentaerythritol triacrylate, 20 parts by weight of urethane acrylate, 55 parts by weight of bisphenol A epoxy resin, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime), 1 part by weight of triarylsulfonium salt, 2 parts by weight of gamma-methacryloxypropyltrimethoxysilane, 2 parts by weight. These components were stirred at 600rpm for 60 minutes at 60 ℃ to give a gum.
The glue was cured with a UV light curing machine and then tested for relevant mechanical properties and shrinkage.
And exposing the glue by using a laser direct writing device, baking the glue for 30min at 100 ℃, developing the glue for 5min by using excessive acetone, finally washing the glue by using isopropanol, and observing the prepared microstructure by using a scanning electron microscope on appearance, resolution, substrate bonding condition, shrinkage and the like.
Comparative example No. three
The components are as follows: 20 parts of pentaerythritol triacrylate, 20 parts of pentaerythritol hexaacrylate, 55 parts of organosilicon-modified bisphenol A epoxy resin (EPSI-6862, epoxy equivalent 550-610g/eq, available from Shanghai Co., ltd., high-tech complexation material) 1 part of 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime), 2 parts of triarylsulfonium salt, and 2 parts of gamma-methacryloxypropyltrimethoxysilane. These components were stirred at 600rpm for 60 minutes at 60 ℃ to give a gum.
The glue is cured by a UV curing machine, and then relevant mechanical properties and shrinkage rate are tested.
And (3) exposing the glue by using a laser direct writing device, baking the glue for 10min at 120 ℃, developing the glue for 5min by using excessive acetone, washing the glue by using isopropanol, and observing the prepared microstructure by using a scanning electron microscope on appearance, resolution, base material bonding condition, shrinkage and the like.
Example one
The components are as follows: 20 parts by weight of pentaerythritol triacrylate, 20 parts by weight of pentaerythritol hexaacrylate, 1 part by weight of an organosilicon-modified bisphenol A epoxy resin 55,1 part by weight of 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime) 1,2 parts by weight of triarylsulfonium salt, and 2 parts by weight of gamma-methacryloxypropyltrimethoxysilane. These components were stirred at 600rpm for 60 minutes at 60 ℃ to give a gum.
The glue was cured with a UV light curing machine and then tested for relevant mechanical properties and shrinkage.
After the glue is exposed by laser direct writing equipment, baking is carried out for 10min at 120 ℃, then excessive acetone is used for developing for 5min, finally isopropanol is used for washing, and then the prepared microstructure is observed by appearance, resolution, base material bonding condition, shrinkage and the like by a scanning electron microscope.
Example two
The components are as follows: 5 parts of epoxy acrylate, 5 parts of ethyl acrylate, 2 parts of organic silicon modified bisphenol A epoxy resin, 80 parts of 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl ] ethanone 1- (O-acetyloxime), 3 parts of triarylsulfonium salt and 2 parts of diethylenetriaminopropyltriethoxysilane. These components were stirred at 600rpm for 60 minutes at 60 ℃ to give a gum.
The glue was cured with a UV light curing machine and then tested for relevant mechanical properties and shrinkage.
The glue is exposed by a laser direct writing device, is dried for 15min at 120 ℃, is developed for 10min by using excessive propylene glycol monomethyl ether acetate, is washed by isopropanol, and is observed in appearance, resolution, base material bonding condition, shrinkage and the like by using a scanning electron microscope.
EXAMPLE III
The components are as follows: 50 parts of pentaerythritol diacrylate, 20 parts of polyurethane acrylate, 3 parts of organic silicon modified bisphenol A epoxy resin, 25 parts of ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2 parts of cumeneferrocene hexafluorophosphate and 2 parts of diethylenetriaminopropyltriethoxysilane. These components were stirred at 600rpm for 60 minutes at 60 ℃ to give a gum.
The glue was cured with a UV light curing machine and then tested for relevant mechanical properties and shrinkage.
The glue is exposed by a laser direct writing device, is baked for 20min at 110 ℃, is developed for 10min by using excessive propylene glycol monomethyl ether acetate, is washed by isopropanol, and is observed by appearance, resolution, base material bonding condition, shrinkage and the like of the prepared microstructure by using a scanning electron microscope.
Example four
The components are as follows: 50 parts of pentaerythritol triacrylate, 20 parts of pentaerythritol hexaacrylate, 1 part of organosilicon-modified cycloaliphatic epoxy resin, 25 parts of 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetoxime), 0.5 part of benzoin bismethyl ether, 2 parts of triarylsulfonium salt and 1.5 parts of gamma-methacryloxypropyltrimethoxysilane. These components were stirred at 600rpm for 60 minutes at 60 ℃ to give a gum.
The glue was cured with a UV light curing machine and then tested for relevant mechanical properties and shrinkage.
And (3) exposing the glue by using a laser direct writing device, baking the glue for 20min at 110 ℃, developing the glue for 5min by using excessive acetone, finally washing the glue by using isopropanol, and observing the prepared microstructure by using a scanning electron microscope on appearance, resolution, base material bonding condition, shrinkage and the like.
EXAMPLE five
The components are as follows: 20 parts of pentaerythritol triacrylate, 20 parts of methyl acrylate, 2 parts of organosilicon-modified cycloaliphatic epoxy resin (55), 1 part of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2 parts of triarylsulfonium salt and 2 parts of diethylenetriaminopropyltriethoxysilane. These components were stirred at 600rpm for 60 minutes at 60 ℃ to give a gum.
The glue is cured by a UV curing machine, and then relevant mechanical properties and shrinkage rate are tested.
The glue is exposed by a laser direct writing device, is baked for 10min at 120 ℃, is developed for 5min by using excessive propylene glycol monomethyl ether acetate, is washed by isopropanol, and is observed by appearance, resolution, base material bonding condition, shrinkage and the like of the prepared microstructure by using a scanning electron microscope.
EXAMPLE six
The components are as follows: 20 parts of pentaerythritol triacrylate, 20 parts of epoxy acrylate, 3 parts of organosilicon-modified cycloaliphatic epoxy resin, 55 parts of 7-diethylamino-3-thiophenecarbonyl coumarin, 1 part of triarylsulfonium salt, 2 parts of gamma-methacryloxypropyltrimethoxysilane and 2 parts of gamma-methacryloxypropyltrimethoxysilane. These components were stirred at 600rpm for 60 minutes at 60 ℃ to give a gum.
The glue was cured with a UV light curing machine and then tested for relevant mechanical properties and shrinkage.
The glue is exposed by a laser direct writing device, is baked for 20min at 120 ℃, is developed for 5min by using excessive propylene glycol monomethyl ether acetate, is washed by isopropanol, and is observed in appearance, resolution, base material bonding condition, shrinkage and the like by using a scanning electron microscope.
The test data pair ratio of the examples and comparative examples is shown in table one.
The photoresist has excellent adhesive force, good bonding with a silicon wafer and lower shrinkage rate; the microstructure prepared by the laser direct writing equipment has smooth appearance and low glue resolution, is suitable for processing and preparing a micro-nano structure, and has good adhesion with a silicon wafer and stable structure and is not easy to fall off.
Claims (10)
1. A solvent-free negative photoresist with high resolution is characterized by comprising the following components in percentage by weight: 10-70% of acrylate monomer, 20-80% of organosilicon modified epoxy resin, 0.5-3% of free radical initiator, 1-5% of cationic initiator and 0.5-2% of adhesion promoter.
2. The solvent-free negative photoresist of claim 1, wherein the acrylate monomer is one or more of methyl acrylate, ethyl acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol hexaacrylate, urethane acrylate, and epoxy acrylate.
3. The solvent-free negative photoresist of claim 1, wherein the silicone-modified epoxy resin is one or more of silicone-modified alicyclic epoxy resin and silicone-modified bisphenol A epoxy resin.
4. The solvent-free negative photoresist according to claim 3, wherein the epoxy equivalent of the silicone-modified epoxy resin is 180 to 320g/eq, and the molecular weight of the silicone segment is 20 to 60% of the total molecular weight.
5. The solvent-free negative photoresist according to any one of claims 1 to 4, wherein the radical initiator is diphenylethanone, α -hydroxyalkylphenone, 2-hydroxy-2-methyl-1-phenylacetone, 1-
Hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2-di
Methylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, benzoin dimethyl ether, benzoin ethyl ether, anthraquinone, thiol, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime),
One or more of 7-diethylamino-3-thenoyl coumarin.
6. The solvent-free negative photoresist of any one of claims 1 to 5, wherein the cationic initiator is one or more of aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron-aryl complexes, cumeneferrocenyl hexafluorophosphate, sulfonyloxyketones, and triarylsiloxy ethers.
7. The solvent-free negative photoresist of any one of claims 1 to 6, wherein the adhesion promoter is one or more of a silicone coupling agent and a modifier thereof, preferably gamma-methacryloxypropyltrimethoxysilane, diaminosilane, vinyltris (beta-methoxyethoxy) silane, glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, vinyltris- (t-butylperoxy) silane, diethylenetriaminopropyltriethoxysilane, phenylaminomethyldimethoxysilane, N, N-bis- (beta-hydroxyethyl) -gamma-aminopropyltriethoxysilane.
8. A solvent-free negative photoresist according to any one of claims 1 to 7, wherein, in use, after laser exposure and before development, post-baking is required, the baking temperature is 100 to 150 ℃, and the baking time is 5 to 30min.
9. A solvent-free negative photoresist according to any of claims 1 to 8, wherein in use, after laser exposure and post-baking, it is developed with a developing solution, which is acetone or propylene glycol methyl ether acetate, and then rinsed with isopropanol.
10. The process of any one of claims 1 to 9, wherein the acrylate monomer, the radical initiator, the silicone modified epoxy resin, the cationic initiator and the adhesion promoter are stirred in a light-tight vessel at a temperature of 40 to 60 ℃ and a speed of 100 to 800rpm for 30 to 120 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110723741.2A CN115542667A (en) | 2021-06-29 | 2021-06-29 | Solvent-free negative photoresist with high resolution and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110723741.2A CN115542667A (en) | 2021-06-29 | 2021-06-29 | Solvent-free negative photoresist with high resolution and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115542667A true CN115542667A (en) | 2022-12-30 |
Family
ID=84717286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110723741.2A Pending CN115542667A (en) | 2021-06-29 | 2021-06-29 | Solvent-free negative photoresist with high resolution and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115542667A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006307087A (en) * | 2005-04-28 | 2006-11-09 | Hitachi Chem Co Ltd | Resin composition, optical member using the same and its manufacturing method |
| CN106243290A (en) * | 2016-05-11 | 2016-12-21 | 杭州乐新材料科技有限公司 | A kind of rubber-type photocuring 3D printed material and preparation method thereof |
| CN112745463A (en) * | 2019-10-31 | 2021-05-04 | 威斯坦(厦门)实业有限公司 | Light-cured resin and preparation method thereof |
-
2021
- 2021-06-29 CN CN202110723741.2A patent/CN115542667A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006307087A (en) * | 2005-04-28 | 2006-11-09 | Hitachi Chem Co Ltd | Resin composition, optical member using the same and its manufacturing method |
| CN106243290A (en) * | 2016-05-11 | 2016-12-21 | 杭州乐新材料科技有限公司 | A kind of rubber-type photocuring 3D printed material and preparation method thereof |
| CN112745463A (en) * | 2019-10-31 | 2021-05-04 | 威斯坦(厦门)实业有限公司 | Light-cured resin and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6093766B2 (en) | Photopolymerizable unsaturated resin, photosensitive resin composition containing the same, and light shielding spacer and liquid crystal display device formed therefrom | |
| TWI453537B (en) | Radiation sensitive resin composition for forming protective film of touch panel and a method for producing the same | |
| TWI254731B (en) | Emission-sensitive composition with variable refractory index and a method for varying refractory index | |
| CN103688221B (en) | Photosensitive polymer combination, solidfied material and sept | |
| US20090324831A1 (en) | Curable resin composition and process for producing cured coating using the same | |
| JP2005325331A (en) | New fluorene-containing resin | |
| CN114621388B (en) | Resin polymer, photo-curing composition and application thereof | |
| CN113929830A (en) | High-heat-resistance 3D printing photosensitive material and preparation method thereof | |
| KR101273993B1 (en) | Polysiloxane composition and process for producing the same, and cured film and process for forming the same | |
| US8414733B2 (en) | Photosensitive resin composition for optical waveguide formation, optical waveguide and method for producing optical waveguide | |
| JP2001083710A (en) | Material for electronic parts and electronic parts obtained by curing the material | |
| KR102312785B1 (en) | Photopolymerizable unsaturated resin, photosensitive resin composition comprising the same, and light shielding spacer and liquid crystal display device formed therefrom | |
| JPWO2008126499A1 (en) | Polymer optical waveguide forming material, polymer optical waveguide, and polymer optical waveguide manufacturing method | |
| CN115542667A (en) | Solvent-free negative photoresist with high resolution and preparation method thereof | |
| JP5076945B2 (en) | Negative radiation sensitive resin composition | |
| JPH1087810A (en) | Photocurable resin composition and production of resin mold | |
| TW201940602A (en) | Photocurable composition for imprinting containing polymer | |
| CN106886128B (en) | Negative photoresist | |
| JP2014174374A (en) | Photosensitive resin composition and cured product of the same | |
| JP2014153411A (en) | Photosensitive resin composition and cured product of the same | |
| JP3321858B2 (en) | Thermosetting resin composition | |
| KR101846555B1 (en) | Curable resin composition comprising organopolysiloxane | |
| TW202244086A (en) | Photocurable liquid composition, cured product, and method for producing cured product | |
| JP2021157176A (en) | Photosensitive resin composition, cured film, substrate with cured film, method for producing substrate with cured film and display device | |
| JPWO2005085922A1 (en) | Manufacturing method of optical waveguide chip |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |