CN105223777A - A kind of stereolithography rapid prototyping mixes type polysiloxane group photosensitive resin composition and its preparation method and application - Google Patents
A kind of stereolithography rapid prototyping mixes type polysiloxane group photosensitive resin composition and its preparation method and application Download PDFInfo
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- CN105223777A CN105223777A CN201410264108.1A CN201410264108A CN105223777A CN 105223777 A CN105223777 A CN 105223777A CN 201410264108 A CN201410264108 A CN 201410264108A CN 105223777 A CN105223777 A CN 105223777A
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- Prior art keywords
- photosensitive resin
- polysiloxane
- methyl
- rapid prototyping
- resin composition
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- -1 polysiloxane group Polymers 0.000 title claims abstract description 93
- 239000011342 resin composition Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000012749 thinning agent Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 10
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 10
- 125000002091 cationic group Chemical group 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 8
- 229920000151 polyglycol Polymers 0.000 claims description 7
- 239000010695 polyglycol Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 5
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims description 4
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 claims description 3
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 claims description 3
- BYRQZFQBDJEADA-UHFFFAOYSA-N 1-(1-phenylpiperazin-2-yl)ethanone Chemical compound C(C)(=O)C1N(CCNC1)C1=CC=CC=C1 BYRQZFQBDJEADA-UHFFFAOYSA-N 0.000 claims description 3
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 3
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical group COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 3
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 claims description 2
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 claims description 2
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 claims description 2
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-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
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 claims description 2
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- XHIKSLHIZYVEQI-UHFFFAOYSA-N CC1=C(C(=O)[PH2]=O)C(=CC(=C1)C)C Chemical compound CC1=C(C(=O)[PH2]=O)C(=CC(=C1)C)C XHIKSLHIZYVEQI-UHFFFAOYSA-N 0.000 claims description 2
- QNJVYPYNVCLCBU-UHFFFAOYSA-N CCOP(=O)C(=O)c1c(C)cc(C)cc1C Chemical compound CCOP(=O)C(=O)c1c(C)cc(C)cc1C QNJVYPYNVCLCBU-UHFFFAOYSA-N 0.000 claims description 2
- ZMDDERVSCYEKPQ-UHFFFAOYSA-N Ethyl (mesitylcarbonyl)phenylphosphinate Chemical compound C=1C=CC=CC=1P(=O)(OCC)C(=O)C1=C(C)C=C(C)C=C1C ZMDDERVSCYEKPQ-UHFFFAOYSA-N 0.000 claims description 2
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 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
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 150000002118 epoxides Chemical group 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- 229960004194 lidocaine Drugs 0.000 claims description 2
- 229950007687 macrogol ester Drugs 0.000 claims description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical class COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 2
- 229920000847 nonoxynol Polymers 0.000 claims description 2
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 claims description 2
- BCWMBWSIQNQIHR-UHFFFAOYSA-N 4-ethyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(CC)CCC2OC21 BCWMBWSIQNQIHR-UHFFFAOYSA-N 0.000 claims 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 5
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 claims 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims 2
- HRDDBYWTPPDWDH-UHFFFAOYSA-N 3-[methyl(trimethylsilyloxy)silyl]propyl 2-methylprop-2-enoate Chemical compound C[SiH](CCCOC(=O)C(C)=C)O[Si](C)(C)C HRDDBYWTPPDWDH-UHFFFAOYSA-N 0.000 claims 1
- MCQIKMFOILBABV-UHFFFAOYSA-N 3-[methyl(trimethylsilyloxy)silyl]propyl prop-2-enoate Chemical compound C(C=C)(=O)OCCC[SiH](C)O[Si](C)(C)C MCQIKMFOILBABV-UHFFFAOYSA-N 0.000 claims 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims 1
- RBEKNHSVDMWRMK-UHFFFAOYSA-N C(C(=C)C)(=O)OCCCC[Si]1(O[Si](O[Si](O1)(C)C)(C)C)C Chemical compound C(C(=C)C)(=O)OCCCC[Si]1(O[Si](O[Si](O1)(C)C)(C)C)C RBEKNHSVDMWRMK-UHFFFAOYSA-N 0.000 claims 1
- RIXILMQBMXMSIS-UHFFFAOYSA-N C(C(=C)C)(=O)OCCCC[Si]1(O[Si](O[Si](O[Si](O1)(C)C)(C)C)(C)C)C Chemical compound C(C(=C)C)(=O)OCCCC[Si]1(O[Si](O[Si](O[Si](O1)(C)C)(C)C)(C)C)C RIXILMQBMXMSIS-UHFFFAOYSA-N 0.000 claims 1
- HDVVTZNLJGUDSK-UHFFFAOYSA-N C(C1CO1)O[SiH](O[Si](C)(C)C)C Chemical compound C(C1CO1)O[SiH](O[Si](C)(C)C)C HDVVTZNLJGUDSK-UHFFFAOYSA-N 0.000 claims 1
- WVSWSKGZGXBAOQ-UHFFFAOYSA-N C(C=C)(=O)OCCCC[Si]1(O[Si](O[Si](O1)(C)C)(C)C)C Chemical compound C(C=C)(=O)OCCCC[Si]1(O[Si](O[Si](O1)(C)C)(C)C)C WVSWSKGZGXBAOQ-UHFFFAOYSA-N 0.000 claims 1
- RQLFSNHQURCNNY-UHFFFAOYSA-N C(C=C)(=O)OCCCC[Si]1(O[Si](O[Si](O[Si](O1)(C)C)(C)C)(C)C)C Chemical compound C(C=C)(=O)OCCCC[Si]1(O[Si](O[Si](O[Si](O1)(C)C)(C)C)(C)C)C RQLFSNHQURCNNY-UHFFFAOYSA-N 0.000 claims 1
- FBEAVZZRKBTLDU-UHFFFAOYSA-N C[Si]1(O[Si](O[Si](O1)(C)COCC2CO2)(C)C)C Chemical compound C[Si]1(O[Si](O[Si](O1)(C)COCC2CO2)(C)C)C FBEAVZZRKBTLDU-UHFFFAOYSA-N 0.000 claims 1
- QNLHGCHRJUEVIT-UHFFFAOYSA-N C[Si]1(O[Si](O[Si](O[Si](O1)(C)C)(C)COCC2CO2)(C)C)C Chemical compound C[Si]1(O[Si](O[Si](O[Si](O1)(C)C)(C)COCC2CO2)(C)C)C QNLHGCHRJUEVIT-UHFFFAOYSA-N 0.000 claims 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims 1
- 239000004359 castor oil Substances 0.000 claims 1
- 235000019438 castor oil Nutrition 0.000 claims 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 238000007493 shaping process Methods 0.000 abstract 1
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 4
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- LJRSZGKUUZPHEB-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxypropoxy)propoxy]propyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COC(C)COC(=O)C=C LJRSZGKUUZPHEB-UHFFFAOYSA-N 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of stereolithography rapid prototyping and mix type polysiloxane group photosensitive resin composition and its preparation method and application, it mainly comprises the material component of following quality proportioning: polysiloxane epoxy resin 20 ~ 70%; Silicone acrylates 10 ~ 45%; Radical initiator 1.0 ~ 4.0%; Cationic initiators 1.0 ~ 6.0%; Polysiloxane thinning agent 10 ~ 60%.By said ratio, raw material is mixed, is heated to transparent liquid under stirring, obtains stereolithography rapid prototyping polysiloxane group photosensitive resin.A kind of stereolithography rapid prototyping of the present invention mixes type polysiloxane group photosensitive resin after stereolithography, has both played the feature of the rapid shaping of photosensitive resin, and has had again the characteristic of the high-low temperature resistant of polysiloxane.The parts utilizing this photosensitive resin to be shaped, have precision high, the advantages such as good heat resistance.
Description
Technical field
The invention belongs to 3D and print Fast Forming Technique field, be specifically related to stereolithography rapid prototyping polysiloxane group photosensitive resin composition and preparation method thereof.
Background technology
3D printing technique is a kind of based on digital model file, uses powdery metal or plastics etc. can jointing material, is carried out the technology of constructed object by the mode successively printed.Meanwhile, 3D printer then appears at the mid-90 in last century, i.e. a kind of rapid molding device of the technology such as utilize photocuring and ply of paper to fold.It is substantially identical with normal printer principle of work, and printer, built with liquid or powder etc. " printed material material ", after being connected, is stacked up " printed material " by conputer controlled from level to level with computer, finally the blueprint on computing machine is become in kind.Nowadays this technology is applied in multiple field, and people manufacture clothes, BUILDINGS MODELS, automobile, chocolate sweets etc. with it.
The principle of work of 3DP is similar to inkjet printing, it is a kind of Rapid Prototyping technique based on drop ejector principle, namely under the excitation of digital signal, the liquid in nozzle operation chamber is made to form drop instantaneously, and spray from nozzle with certain speed and frequency, be ejected into assigned address, successively pile up after solidification, obtain formation of parts.
Print as 3D of new generation, use liquid photosensitive resin molded part, be cured with ultraviolet light.Do not need expensive laser system, therefore equipment price is cheap, and operation and maintenance cost is also very low, can work at lower temperature (minimum reach 50 DEG C); And, also have simple to operate, forming speed is fast, forming process is pollution-free, the precision of drip molding is high, can in advantages such as office environment uses, therefore, application prospect is very good.
The viscosity being applicable to the photosensitive resin requirement glue system that 3D prints is low, and good fluidity, solidification rate is fast, and cure shrinkage is low, and goods are bent without sled, the requirements such as excellent heat resistance.At present, the domestic preparation method for high precision, high-fire resistance stereolithography rapid prototyping material reports less.Report is had no specific to stereolithography rapid prototyping polysiloxane group photosensitive resin and preparation thereof.
Summary of the invention
The object of the present invention is to provide a kind of high precision, high-fire resistance stereolithography rapid prototyping polysiloxane group photosensitive resin.The light-sensitive emulsion glassware for drinking water adopting this technology to prepare has system viscosity low, the advantage of good fluidity, under UV-irradiation, have glue curing speed fast, cure shrinkage is low, and goods are without the characteristic of sled song, due to the agent structure of its polysiloxane, give the high-low temperature resistant characteristic of the rear goods excellence of solidification.The parts utilizing this polysiloxane group photosensitive resin to be shaped, have precision high, the advantages such as good heat resistance.
The present invention also aims to the manufacture method that stereolithography rapid prototyping polysiloxane group photosensitive resin is provided.
The present invention is achieved through the following technical solutions:
A kind of stereolithography rapid prototyping mixes type polysiloxane group photosensitive resin composition, comprises the material component of following quality proportioning:
Polysiloxane epoxy resin 20 ~ 70%;
Silicone acrylates 10 ~ 45%;
Radical initiator 1.0 ~ 4.0%;
Cationic initiators 1.0 ~ 6.0%;
Thinning agent 10 ~ 60%
Preferably, described polysiloxane epoxy resin is the polysiloxane or 2 of allyl glycidyl ether modification, 3-epoxy-5-vinyl norbornene modified polyorganosiloxane or 4-vinyl cyclohexene oxide modified polyorganosiloxane, molecular weight is between 300-50000, uses one or more used in combination respectively.
Preferably, described silicone acrylates is that molecular weight is between 300-50000, uses one or more used in combination respectively containing the polysiloxane of γ-methacryloxypropyl or the polysiloxane of acryloxypropyl.
Preferably, described thinning agent is containing the thinning agent of epoxide group, acrylate diluent or their potpourri.
More preferably, described epoxy resin diluent is trihydroxymethylpropanyltri diglycidyl ether, the polysiloxane of the allyl glycidyl ether modification of low polymerization degree, 2 of low polymerization degree, 3-epoxy-5-vinyl norbornene modified polyorganosiloxane, the 4-vinyl cyclohexene oxide modified polyorganosiloxane of low polymerization degree, the preferred degree of polymerization is between 2-20, described acrylate diluent is lauryl acrylate, ethoxyethyl acrylate, ethoxyethoxy ethyl acrylate, diacrylate diglycol ester, trimethyol propane triacrylate, Nonyl phenol ethoxylate acrylate, Isooctyl acrylate monomer, methacrylic acid-beta-hydroxy ethyl ester, 1, 6-hexanediyl ester, tri (propylene glycol) diacrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, the polysiloxane of the γ-methacryloxypropyl of two contracting trihydroxy methyl four (methyl) acrylate or their potpourri or low polymerization degree, the polysiloxane of the acryloxypropyl of low polymerization degree, the preferred degree of polymerization is between 2-20.
Preferably, described radical initiator is the radical initiator causing silicone acrylates; Described cationic initiators is the cationic initiators causing polysiloxane polymerization of epoxy resins.
More preferably, described radical initiator is methyl benzoylformate, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-1-acetone, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl) phenyl]-1-butanone, 2, 4, 6-trimethylbenzoyl phenyl phosphinic acid ethyl ester, 2, 4, 6-trimethylbenzoy-dipheny phosphine oxide, 2-methyl-2-(4-morpholinyl)-1-[4-(methyl mercapto) phenyl]-1-acetone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylacetone, polymerization [2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone, 2-isopropyl thioxanthone, 2, 4-diethyl thioxanthone, 4-phenyl benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-(dimethylamino)-benzoic acid-(2-ethyl) own ester, EDMAB, 2, 2-dimethoxy-1, 2-benzyl phenyl ketone, 4-methyl benzophenone, benzophenone, 4, 4 '-two (lignocaine) benzophenone, o-benzoyl yl benzoic acid macrogol ester, polyglycol two (β-4-[to (2-dimethyl amine-2-benzyl) bytyry phenyl] piperazine) propionic ester, polyglycol two (β-4-is to acetylphenyl-piperazine) propionic ester, polyglycol two-(p-dimethylaminobenzoic acid) ester, polytetramethylene glycol 250 2-(2-carboxymethoxyl thioxanthones) ester, polytetramethylene glycol 250-(4-benzoyl phenoxy acetic acid) ester, the two benzoyl formiate of polytetramethylene glycol or two or more potpourri in them.
More preferably, described cationic initiators is two 2, the luxuriant titanium of 6-bis-fluoro-3-pyrroles phenyl two, triaryl hexafluorophosphoric acid sulfosalt, 4, 4 '-dimethyl diphenyl iodine hexafluorophosphate, 10-(4-xenyl)-ITX hexafluorophosphate, the reaction product of the same 10-of polyvalent alcohol [4-(2-carboxymethoxyl)-biphenyl]-2-isopropyl-9 oxygen-9H-thioxanthones-10-sulphur hexafluorophosphate, phenyl two (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2, 4, 6-trimethylbenzoy-dipheny phosphine oxide, 2, 4, 6-trimethylbenzoyl phosphinic acid ethyl ester or potpourris two or more in them.
Present invention also offers the preparation method that a kind of above-mentioned stereolithography rapid prototyping mixes type polysiloxane group photosensitive resin, the method is mixed by described quality proportioning by described material component, mixture is heated, stir till becoming transparent faint yellow uniform liquid, the product of acquisition is stereolithography rapid prototyping photosensitive resin.
Above-mentioned stereolithography rapid prototyping mixes type polysiloxane group photosensitive resin and is applied to stereolithography rapid prototyping technical field as photo-curing material, and its curing light source preferably adopts wavelength to be the ultraviolet light of 355nm ~ 385nmnm.
Embodiment
Below in conjunction with embodiment, the present invention is done and describes in detail further, but implementation of the present invention is not limited thereto.
Embodiment 1
In the glass there-necked flask of 5000 milliliters that stirrer and condenser pipe are housed, add polysiloxane (molecular weight about the 500) 1042g of allyl glycidyl ether modification, polysiloxane (molecular weight about the 50000) 720.0g of γ-methacryloxypropyl, polysiloxane (degree of polymerization the is 5) 480.0g of the allyl glycidyl ether modification of thinning agent low polymerization degree, tri (propylene glycol) diacrylate 480.0g, methyl benzoylformate 64 grams, the luxuriant titanium of two 2,6-bis-fluoro-3-pyrroles's phenyl two 96 grams.Heating, stir until become transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.
Embodiment 2
In the glass there-necked flask of 5000 milliliters that stirrer and condenser pipe are housed; add 2; 3-epoxy-5-vinyl norbornene modified polyorganosiloxane (molecular weight about 50000) 2000g; polysiloxane (molecular weight about the 500) 1000g of acryloxypropyl; 2 of thinning agent low polymerization degree; 3-epoxy-5-vinyl norbornene modified polyorganosiloxane (degree of polymerization is 20) 500g; 2; 4; 6-trimethylbenzoy-dipheny phosphine oxide 100g, triaryl hexafluorophosphoric acid sulfosalt 100 grams.Heating, stir until become transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.
Embodiment 3
In the glass there-necked flask of 5000 milliliters that stirrer and condenser pipe are housed, add 4-vinyl cyclohexene oxide modified polyorganosiloxane (molecular weight about 30000) 1500.0g, polysiloxane (molecular weight about the 12000) 1200.0g of methacryloxypropyl, 4-vinyl cyclohexene oxide modified polyorganosiloxane (degree of polymerization the is 10) 800.0g of thinning agent low polymerization degree, two contracting trihydroxy methyl four (methyl) acrylate 300.0g, 4-methyl benzophenone 65.0g, 10-(4-xenyl)-ITX hexafluorophosphate 75.0 grams.Heating, stir until become transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.
Embodiment 4
In the glass there-necked flask of 5000 milliliters that stirrer and condenser pipe are housed, add 4-vinyl cyclohexene oxide modified polyorganosiloxane (molecular weight about 30000) 800g, 2, 3-epoxy-5-vinyl norbornene modified polyorganosiloxane (molecular weight about 50000) 200.0g, polysiloxane (molecular weight about the 1000) 1200g of methacryloxypropyl, polysiloxane (molecular weight about the 3000) 220g of acryloxypropyl, thinning agent Isooctyl acrylate monomer 350.0g and methacrylic acid-beta-hydroxy ethyl ester 400.0g, polyglycol two (β-4-is to acetylphenyl-piperazine) propionic ester 85.0g, 10-(4-xenyl)-ITX hexafluorophosphate 70.0 grams.Heating, stir until become transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.
Embodiment 5
In the glass there-necked flask of 5000 milliliters that stirrer and condenser pipe are housed, add 2, 3-epoxy-5-vinyl norbornene modified polyorganosiloxane (molecular weight about 12000) 600.0g, with 4-vinyl cyclohexene oxide modified polyorganosiloxane (molecular weight about 10000) 800g, 4-vinyl cyclohexene oxide modified polyorganosiloxane (degree of polymerization 8) 700.0g of low polymerization degree, thinning agent trimethyol propane triacrylate 400.0g, two contracting trihydroxy methyl four (methyl) acrylate 300.0g, polymerization [2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone, 2-isopropyl thioxanthone 100.0g, the reaction product 60.0 grams of the same 10-of polyvalent alcohol [4-(2-carboxymethoxyl)-biphenyl]-2-isopropyl-9 oxygen-9H-thioxanthones-10-sulphur hexafluorophosphate.Heating, stir until become transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included in protection model of the present invention.
Claims (10)
1. stereolithography rapid prototyping mixes a type polysiloxane group photosensitive resin composition, it is characterized in that: the material component comprising following quality proportioning:
Polysiloxane epoxy resin 20 ~ 70%;
Silicone acrylates 10 ~ 45%;
Radical initiator 1.0 ~ 4.0%;
Cationic initiators 1.0 ~ 6.0%;
Polysiloxane thinning agent 10 ~ 60%;
Thinning agent 10-60%.
2. a kind of stereolithography rapid prototyping according to claim 1 mixes type polysiloxane group photosensitive resin composition, it is characterized in that: described polysiloxane epoxy resin is polysiloxane backbone, side base or (with) end group contains the polysiloxane epoxy resin of epoxide group, also referred to as epoxy-modified polysiloxane, molecular weight is between 100-50000.
3. a kind of stereolithography rapid prototyping according to claim 1 mixes type polysiloxane group photosensitive resin composition, it is characterized in that: described silicone acrylates is polysiloxane is main chain, side base or (with) end group contains the silicone acrylates resin of (methyl) acryloxypropyl group, also be referred to as meaning acryloxypropyl modified polyorganosiloxane, molecular weight is between 100-50000.
4. a kind of stereolithography rapid prototyping according to claim 1 mixes type polysiloxane group photosensitive resin composition, it is characterized in that: described thinning agent is alkyl glycidyl ether, neodecanoic acid diglycidyl fat, trihydroxymethylpropanyltri diglycidyl ether, toluene glycidol ether, castor oil polyglycidyl ether, lauryl acrylate, ethoxyethyl acrylate, ethoxyethoxy ethyl acrylate, diacrylate diglycol ester, trimethyol propane triacrylate, Nonyl phenol ethoxylate acrylate, Isooctyl acrylate monomer, methacrylic acid-beta-hydroxy ethyl ester, 1, 6-hexanediyl ester, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, the epoxy resin diluents such as two contracting trihydroxy methyl four (methyl) acrylate and acrylate diluent or their potpourri.
5. a kind of stereolithography rapid prototyping according to claim 1 mixes type polysiloxane group photosensitive resin composition, it is characterized in that: described polysiloxane thinning agent is two (2,3-epoxypropoxy) tetramethyl disiloxane, two (2,3-epoxypropoxy) hexam ethylcyclotrisiloxane, two (2,3-epoxypropoxy) octamethylcyclotetrasiloxane, two (2,3-epoxypropoxy) decamethyl five siloxane, two (4-ethyl cyclohexene oxide) tetramethyl disiloxane, two (4-ethyl cyclohexene oxide) hexam ethylcyclotrisiloxane, two (4-ethyl cyclohexene oxide) octamethylcyclotetrasiloxane, two (4-ethyl cyclohexene oxide) decamethyl five siloxane, two (2,3-epoxy-5-ethyl norbornene) tetramethyl disiloxane, two (2,3-epoxy-5-ethyl norbornene) hexam ethylcyclotrisiloxane, two (2,3-epoxy-5-ethyl norbornene) octamethylcyclotetrasiloxane, two (2,3-epoxy-5-ethyl norbornene) decamethyl five siloxane, four (2,3-epoxypropoxy) tetramethyl-ring tetrasiloxane, four (4-ethyl cyclohexene oxide) tetramethyl-ring tetrasiloxane, four (2,3-epoxy-5-ethyl norbornene) tetramethyl-ring tetrasiloxane, two (acryloxypropyl) tetramethyl disiloxane, two (acryloxypropyl) hexam ethylcyclotrisiloxane, two (acryloxypropyl) octamethylcyclotetrasiloxane, two (acryloxypropyl) decamethyl five siloxane, two (methacryloxypropyl) tetramethyl disiloxane, two (methacryloxypropyl) hexam ethylcyclotrisiloxane, two (methacryloxypropyl) octamethylcyclotetrasiloxane, two (methacryloxypropyl) decamethyl five siloxane, four (acryloxypropyl) tetramethyl-ring tetrasiloxane, four (methacryloxypropyl) tetramethyl-ring tetrasiloxane, or more the potpourri of material.
6. a kind of stereolithography rapid prototyping according to claim 1 mixes type polysiloxane group photosensitive resin composition, it is characterized in that: described radical initiator is the radical initiator of initiating methacrylates polymerization, and described cationic initiators causes the cationic initiators of polymerization of epoxy resins.
7. a kind of stereolithography rapid prototyping according to claim 6 mixes type polysiloxane group photosensitive resin composition, it is characterized in that: described radical initiator is methyl benzoylformate, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-1-acetone, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl) phenyl]-1-butanone, 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester, 2,4,6-trimethylbenzoy-dipheny phosphine oxide, 2-methyl-2-(4-morpholinyl)-1-[4-(methyl mercapto) phenyl]-1-acetone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylacetone, polymerization [2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 4-phenyl benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-(dimethylamino)-benzoic acid-(2-ethyl) own ester, EDMAB, 2,2-dimethoxy-1,2-benzyl phenyl ketone, 4-methyl benzophenone, benzophenone, 4,4 '-two (lignocaine) benzophenone, o-benzoyl yl benzoic acid macrogol ester, polyglycol two (β-4-[to (2-dimethyl amine-2-benzyl) bytyry phenyl] piperazine) propionic ester, polyglycol two (β-4-is to acetylphenyl-piperazine) propionic ester, polyglycol two-(p-dimethylaminobenzoic acid) ester, polytetramethylene glycol 250 2-(2-carboxymethoxyl thioxanthones) ester, polytetramethylene glycol 250-(4-benzoyl phenoxy acetic acid) ester, the two benzoyl formiate of polytetramethylene glycol or two or more potpourri in them.
8. a kind of stereolithography rapid prototyping according to claim 6 mixes type polysiloxane group photosensitive resin composition, it is characterized in that: described cationic initiators is two 2, the luxuriant titanium of 6-bis-fluoro-3-pyrroles phenyl two, triaryl hexafluorophosphoric acid sulfosalt, 4, 4 '-dimethyl diphenyl iodine hexafluorophosphate, 10-(4-xenyl)-ITX hexafluorophosphate, the reaction product of the same 10-of polyvalent alcohol [4-(2-carboxymethoxyl)-biphenyl]-2-isopropyl-9 oxygen-9H-thioxanthones-10-sulphur hexafluorophosphate, phenyl two (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2, 4, 6-trimethylbenzoy-dipheny phosphine oxide, 2, 4, 6-trimethylbenzoyl phosphinic acid ethyl ester or potpourris two or more in them.
9. a kind of stereolithography rapid prototyping according to claim 1-8 mixes the preparation method of type polysiloxane group photosensitive resin composition, it is characterized in that: described material component is mixed by described quality proportioning, stir lower heating, until become transparent uniform liquid.
10. a kind of stereolithography rapid prototyping described in claim 1-9 mixes the application of type polysiloxane group photosensitive resin composition, it is characterized in that: curing light source adopts wavelength to be the ultraviolet light of 355nm ~ 385nmnm.
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| CN109970450A (en) * | 2019-03-28 | 2019-07-05 | 天津大学 | A kind of light sensitive ceramics liquid and its ceramic member for 3D printing |
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