CN112778447A - Soluble photosensitive resin and preparation method thereof and cured lamination inhibition method - Google Patents
Soluble photosensitive resin and preparation method thereof and cured lamination inhibition method Download PDFInfo
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- CN112778447A CN112778447A CN202011639304.4A CN202011639304A CN112778447A CN 112778447 A CN112778447 A CN 112778447A CN 202011639304 A CN202011639304 A CN 202011639304A CN 112778447 A CN112778447 A CN 112778447A
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- photosensitive resin
- parts
- agent
- stirring
- light
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- 239000011347 resin Substances 0.000 title claims abstract description 121
- 229920005989 resin Polymers 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 230000005764 inhibitory process Effects 0.000 title abstract description 14
- 238000003475 lamination Methods 0.000 title abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 238000005336 cracking Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 23
- 238000000465 moulding Methods 0.000 claims abstract description 22
- 230000001276 controlling effect Effects 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 17
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 14
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000012949 free radical photoinitiator Substances 0.000 claims abstract description 10
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 10
- 238000004090 dissolution Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 24
- 238000002791 soaking Methods 0.000 claims description 22
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- 238000004140 cleaning Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003682 fluorination reaction Methods 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 9
- MRQIXHXHHPWVIL-UHFFFAOYSA-N chembl1397023 Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC1=CC=CC=C1 MRQIXHXHHPWVIL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010453 quartz Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 7
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 230000007613 environmental effect Effects 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 4
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- NWWQVENFTIRUMF-UHFFFAOYSA-N diphenylphosphanyl 2,4,6-trimethylbenzoate Chemical compound CC1=CC(C)=CC(C)=C1C(=O)OP(C=1C=CC=CC=1)C1=CC=CC=C1 NWWQVENFTIRUMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 3
- 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
- HEBDGRTWECSNNT-UHFFFAOYSA-N 2-methylidenepentanoic acid Chemical compound CCCC(=C)C(O)=O HEBDGRTWECSNNT-UHFFFAOYSA-N 0.000 claims description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 235000010981 methylcellulose Nutrition 0.000 claims description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 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
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 claims description 3
- 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 claims description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 claims 2
- 230000036211 photosensitivity Effects 0.000 claims 2
- 150000002576 ketones Chemical class 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 claims 1
- 238000010146 3D printing Methods 0.000 abstract description 22
- 230000002401 inhibitory effect Effects 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000007639 printing Methods 0.000 abstract description 2
- 238000003672 processing method Methods 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 40
- 239000000243 solution Substances 0.000 description 36
- 238000012545 processing Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000003860 storage Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 3
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000110 selective laser sintering Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
- C08K5/08—Quinones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
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- Engineering & Computer Science (AREA)
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- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
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- Ceramic Engineering (AREA)
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- Electrochemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
A soluble photosensitive resin and a preparation and curing lamination inhibition method thereof, the raw materials comprise, by mass, 70-80 parts of low polymer polyacrylamide ester, 5-10 parts of crosslinking type cracking agent, 9-12 parts of high polymer linking agent, 3-5 parts of cracking type free radical photoinitiator, 2-6 parts of light-resistant agent for regulating and controlling molding precision, and 0.05 part of polymerization inhibitor, so that the molding precision is improved to 80um while high-efficiency manufacturing and environment-friendly dissolution are met; the method for eliminating the interlamellar lines comprises the steps of treating and inhibiting the interlamellar lines after solidification in liquid so as to improve the surface smoothness of the printing structure; the invention has stable property, simple preparation process, stronger photosensitive characteristic in the range of 365nm to 425nm, and adjustable photosensitive property and mechanical property, and obtains a complex three-dimensional structure for indirect 3D printing; in addition, the lamellar texture eliminating method is beneficial to demolding and improving the surface quality in the indirect rollover forming process of the three-dimensional structure, and is a key processing method for realizing three-dimensional inverse structure forming based on Boolean operation.
Description
Technical Field
The invention belongs to the technical field of additive manufacturing, particularly relates to a soluble photosensitive resin suitable for high-precision indirect 3D printing and a preparation method and a cured lamination inhibition method thereof, and particularly provides a high-precision multi-component wide-sensitivity-range soluble resin suitable for 365nm to 425nm ultraviolet light regions and a preparation method thereof, and a lamination inhibition method for processing a step effect of a molding surface.
Background
At present, key parts of core devices in various fields such as military and civil use are gradually developing towards the directions of function integration, micro-precision, complex appearance and the like, and the manufacturing of related microstructures also embodies the characteristics of various application materials, complex process, high-precision three-dimensional forming and the like. In recent years, an additive manufacturing (3D printing) technology characterized by material "discrete-accumulation" has become an important way to improve or optimize the manufacturing performance of functional parts, and the advantages of large design dimension, high manufacturing efficiency, data integration and the like provide convenience for high-precision molding of complex microstructures, and expand the designable space and molding range of three-dimensional microstructures.
However, for microstructure molding materials with different properties, the process capabilities of layering, extrusion, curing, accumulation and the like are different, the manufacturing of the related cantilever beam, hollow, porous and other structures is still a technical difficulty of the 3D printing process, and for typical processes such as laser fused deposition, selective laser sintering, photocuring accumulation molding and the like, the support structure is still required to be arranged in the molding direction to ensure the integrity of structure printing.
Aiming at the problems of mismatching of materials and processes, mismatching of design range and manufacturing capability and the like in the traditional 3D printing process, the indirect photocuring 3D printing technology provides a solution for rapid forming and performance optimization of materials difficult to form. According to the method, the manufacturing efficiency of the complex structure can be improved through the rapid material removal and three-dimensional template auxiliary forming process, and the support material is removed by the methods of dissolution, ablation, stripping and the like after the high polymer material is cured, so that the forming performance of the high-performance material is improved, and the material which is easy to form and difficult to form is improved.
With the development of high molecular materials and photochemical technologies, the development of soluble photosensitive resins is the technical basis for realizing the indirect photocuring 3D printing process. In terms of forming precision, most of the existing soluble photosensitive resins use acrylic-based chain segment crosslinking as a basic composition of a high polymer material system, and the highest forming precision which can be achieved in terms of forming precision is only 500 micrometers, so that the forming requirement of a high-precision three-dimensional microstructure cannot be met.
In terms of material composition and dissolution efficiency, the photosensitive resin which meets the high-precision forming quality cannot be dissolved in a common organic solvent because a condensation bond in a high-molecular chain segment is a chemical single bond, and the forming material containing a breaking bond cannot meet the precision requirement of three-dimensional microstructure manufacturing, and in crosslinking systems such as an acrylic group, an NVP group, a PEGMA group and the like, the material removal rate can only reach about 50%, and the high removal rate cannot be realized in a turnover process of a three-dimensional microporous structure, so that the indirect manufacturing efficiency is seriously influenced. In the selection of the dissolving agent, most of the degrading agents of the soluble resin are organic solvents, so that the environment is harmful and the human-computer compatibility is not good; on the aspects of material properties and forming characteristics, most of soluble photosensitive resin has a narrow photosensitive range, the forming quality of a microstructure has strong dependence on a light machine, the forming mechanical strength is poor, and the operability of a material pouring process is further restricted on microstructure support. In the aspect of forming quality, most of soluble resin prepared from single components is sensitive to natural light due to characteristics of material composition, and is easy to generate the phenomena of unstable properties such as self-crosslinking, material volatilization or sedimentation, and the like.
Therefore, according to the reported data, it is difficult to draw a conclusion that the existing soluble photosensitive resin can not simultaneously meet the requirements of quick dissolution and high-precision molding, and the two requirements are the core process requirements of indirect molding of the three-dimensional microstructure. In order to expand the environmental adaptability of the soluble photosensitive resin to the 3D printing process, improve the forming precision and the dissolving efficiency and improve the surface quality of the three-dimensional structure in a microscale, the soluble photosensitive resin with high dissolving rate, high precision, wide photosensitive range, adjustable component performance and stable performance needs to be developed, a 3D printing step effect-oriented lamellar inhibition method is developed, and a material basis and a process realization scheme are provided for indirect forming of a high-precision and high-quality three-dimensional microstructure.
Disclosure of Invention
In order to improve the forming precision, the dissolving efficiency, the stability and the performance controllability of the soluble photosensitive resin and solve the problem of the mismatching of the forming precision, the dissolving rate, the mechanical performance, the photosensitive range and other attributes of the existing soluble photosensitive resin, the invention aims to provide the soluble photosensitive resin, the preparation method thereof and the cured lamination inhibition method thereof, the forming dimension of indirect 3D printing is improved, and the step effect lamination inhibition method is provided aiming at the step effect of the surface of a microstructure in the common photosensitive resin 3D printing process.
In order to achieve the purpose, the invention provides a specific scheme as follows:
the soluble photosensitive resin comprises, by mass, 70-80 parts of oligomer polyacrylamide ester, 5-10 parts of a crosslinking type cracking agent, 9-12 parts of a high-molecular connecting agent, 3-5 parts of a cracking type free radical photoinitiator and 2-6 parts of a light-blocking agent for regulating and controlling molding precision.
Preferably, the raw material also comprises 0.05 part of polymerization inhibitor, and the polymerization inhibitor is one of p-hydroxyanisole and hydroquinone.
The oligomer polyacrylamide ester is pre-polymerized by adopting an acrylic group and an acrylamide group in any proportion, wherein the acrylic group at least comprises one or more of acrylic acid, methacrylic acid, 2-ethacrylic acid and 2-propylacrylic acid; the acrylamide group at least comprises one of acrylamide, hydroxymethyl acrylamide, dimethylacrylamide, N-dimethylacrylamide and N, N-methylene bisacrylamide.
The composition of the oligomeric polyacrylamide ester also includes an oligomer that has been synthesized, including urethane acrylate, polyester acrylamide ester, polyester acrylate, methyl acrylate, ethyl acrylate, and one of monofunctional N-vinyl pyrrolidone, multifunctional polyethylene glycol dimethacrylate.
The crosslinking cracking agent at least comprises one of methacrylic anhydride and N, N-methylene bisacrylamide.
The high-molecular connecting agent comprises one of carboxymethyl cellulose, N-methyl pyrrolidone, polyvinylpyrrolidone, sodium polyacrylate, methyl cellulose, sodium carboxymethyl cellulose and sodium polyacrylate.
The cracking free radical photoinitiator contains one or more of acylphosphine oxides, alpha-hydroxyalkyl benzones and alpha-amine alkyl benzones, so that the matching capability of photosensitive resin in a photosensitive range of 365-425 nm can be regulated and controlled by different component ratios.
The photosensitive resin is prepared by compounding acylphosphine oxides and alpha-hydroxyalkyl phenone initiators to reach a photosensitive range within a wavelength range of 365-.
The photosensitive resin is compounded by selecting acylphosphine oxides and alpha-amine alkyl benzone initiators to achieve the photosensitive range within the wavelength range of 385nm to 425nm, the acylphosphine oxides comprise at least one of diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, bis (2, 6-methoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide, the alpha-amine alkyl benzone initiator at least comprises one of 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-acetone and 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone.
The light-blocking agent at least comprises one of azo group or phenolic hydroxyl color-aiding group, and the light-blocking agent containing azo group chromophore at least selects one of phenylazo-2-naphthol, sodium p-dimethylaminoazobenzenesulfonate and methylene blue; optionally, the light-blocking agent containing the phenolic hydroxyl chromophore is at least one selected from the group consisting of phenylazo-2-naphthol, 1, 4-dihydroxyanthraquinone, 2-hydroxybenzophenone and 2, 6-dihydroxydibenzocyclohexanone.
The preparation method based on the soluble photosensitive resin comprises the following steps:
(1) in an anaerobic drying environment, hermetically stirring the mixture of the oligomer polyacrylamide ester and the polymerization inhibitor until a prepolymer liquid which is uniformly mixed and clarified is obtained;
(2) preheating a high-molecular connecting agent to 60-80 ℃ in a heating dish, grinding, adding the high-molecular connecting agent into the prepolymer while stirring, and uniformly mixing to obtain a first-stage composition with mechanical properties and high-molecular crosslinking properties;
(3) selecting a light-resistant condition, keeping the stirring state, sequentially adding a light-resistant agent, a cracking type free radical photoinitiator and a crosslinking type cracking agent, keeping the temperature of the resin constant at 50-70 ℃, uniformly mixing until the color of the resin is clear and transparent, and storing the resin product in a brown quartz vessel in a sealing manner.
The oxygen content in the anaerobic drying environment in the step (1) is reduced to be below 1500ppm, the relative humidity is reduced to be below 10 percent, or dry nitrogen or argon is introduced into a stirring environment.
The environmental temperature in the step (1) is controlled to be kept at 45-65 ℃, the stirring speed cannot exceed 2000rpm, and the stirring time is not less than 1 hour.
The stirring speed in the step (2) is 500-2500rpm, and the stirring time is 2-4 hours.
Adding the high molecular connecting agent in the step (2) and adding the light-blocking agent in the step (3) need to be applied from the position with the fastest stirring flow speed;
and (3) adding the photoinitiator after the light-resisting agent is uniformly dispersed.
The stirring adopts a magnetic stirrer.
The heating adopts a constant temperature oil bath heating pan.
A method for inhibiting cured lamination of soluble photosensitive resin comprises the following steps:
(1) placing the cured and molded part in an electrolytic fluorination liquid, soaking for 10-15 minutes, and removing the photosensitive resin remained on the surface to show the molding effect of the curved surface step after molding;
(2) taking out the electronic fluoridizing liquid, cleaning the surface of the electronic fluoridizing liquid in deionized water, soaking the electronic fluoridizing liquid in an ethanol solution of sodium hydroxide, adjusting the soaking time according to the surface etching effect, taking out the electronic fluoridizing liquid, and placing the electronic fluoridizing liquid for cleaning;
(3) and (3) carrying out surface drying treatment on the treated molded part in a vacuum drying oven, controlling the treatment temperature to be 70-90 ℃, controlling the treatment time to be within 20 minutes, taking out and storing in a drying environment.
The solidified molded part needs to be soaked in electrolytic fluoride liquid or ethanol solution of sodium hydroxide, and the solution is not less than 20 times of the volume of the solidified part in the two soaking processes, so that the solidified molded part is completely soaked in the liquid for treatment.
The electrolytic fluorination liquid in the step (1) is one of FC-40, FMD-50 or FMD-120, and the surface of the large-area molded part is treated by adopting hydrofluoroether electronic fluorination liquid.
In the step (2), the concentration of the sodium hydroxide alcoholic solution is controlled to be 0.1-0.25 mol/L, and the dissolution temperature of the sodium hydroxide powder is controlled to be 60-80 ℃.
The invention has the beneficial effects that:
(1) the soluble photosensitive resin can realize high-precision 3D printing in different ultraviolet wavelength adjusting ranges, the forming precision of a three-dimensional structure can be improved to 80um, and the soluble photosensitive resin is used for manufacturing an inverse structure three-dimensional microstructure based on Boolean operation and is a material realization basis for indirect 3D printing.
(2) The soluble photosensitive resin disclosed by the invention is simple in preparation process, wide in material source, easy to realize in material synthesis environment, low in dissolving environment requirement, high in dissolving efficiency, small in environmental pollution, stable in performance of resin materials and dissolving materials and long in storage time, and can be used for quickly preparing and dissolving resin with high yield.
(3) The light-resisting agent in the soluble resin can quantitatively regulate and control the forming process and the forming precision, as shown in an influence curve of the selection of different light-resisting agents on the forming precision in figure 2; the matching of the soluble photosensitive resin and different devices can be quantitatively regulated and controlled by compounding the cracking type photoinitiator, as shown in different photoinitiator compositions and ultraviolet light sensitive peak positions in figure 3, the molding conditions of the material and the allowable range of corresponding 3D printing equipment are expanded.
(4) The method for inhibiting the striations of the soluble resin photocuring 3D printing formed part has a high-efficiency step effect inhibiting effect, and is beneficial to improvement of surface quality after demolding of a three-dimensional structure and forming of an inverse structure.
Drawings
Fig. 1 is a schematic diagram of effects that can be achieved by the method for suppressing the striations provided in the embodiment of the present invention.
FIG. 2 is a graph showing the effect of selection of different light blockers on molding accuracy as provided in the present disclosure.
FIG. 3 is a graph of the effect of selection of different photoinitiators provided in the context of the present invention on the UV light sensitivity range.
Fig. 4 is a scanning electron microscope image of a microstructure of three different material compositions according to an embodiment of the present invention, wherein (a) in fig. 4 is a scanning electron microscope image of a microstructure of a second embodiment, fig. 4(b) is a scanning electron microscope image of a microstructure of a fourth embodiment, and fig. 4(c) is a scanning electron microscope image of a microstructure of a fifth embodiment.
FIG. 5 is a graph showing the comparison of the transmittance of a resin with that of a high-precision insoluble resin used in an example of the present invention.
FIG. 6 shows the relationship between shrinkage during curing and molding and the cracking agent in the material composition.
FIG. 7 is a comparison of surface topography before and after a comparative ply removal treatment in an example of the invention.
FIG. 8 is a schematic flow chart of the preparation and striation inhibition of the present invention.
Detailed Description
The present invention will be described in further detail with reference to preferred examples thereof.
The soluble photosensitive resin comprises, by mass, 70-80 parts of oligomer polyacrylamide ester, 5-10 parts of a crosslinking type cracking agent, 9-12 parts of a high-molecular connecting agent, 3-5 parts of a cracking type free radical photoinitiator and 2-6 parts of a light-blocking agent for regulating and controlling molding precision.
Preferably, 0.05 part of polymerization inhibitor is added into the photosensitive resin system for improving the quality stability of the soluble photosensitive resin during storage and use and preventing self-polymerization, and the polymerization inhibitor is one of p-hydroxyanisole and hydroquinone.
The principle of the high-precision soluble photosensitive resin is that a high-molecular oligomer network consisting of a crosslinking cracking agent can hydrolyze the cracking agent in an alkaline environment, and the degradation of the high-molecular network into a high-molecular long chain is promoted due to the forward progress of a hydrolysis reaction. In addition, different kinds of light blocking agents and photoinitiators are adopted in the invention, and the reflection and absorption effects of the soluble photosensitive resin on ultraviolet light initiated free radicals can be respectively regulated and controlled under the interaction of the composite proportion, so that the forming precision is improved.
The oligomer polyacrylamide ester is pre-polymerized by adopting an acrylic group and an acrylamide group in any proportion, wherein the acrylic group at least comprises one or more of acrylic acid, methacrylic acid, 2-ethacrylic acid and 2-propylacrylic acid; the acrylamide group at least comprises one of acrylamide, hydroxymethyl acrylamide, dimethylacrylamide, N-dimethylacrylamide and N, N-methylene bisacrylamide.
The composition of the oligomeric polyacrylamide ester also includes an oligomer that has been synthesized, including urethane acrylate, polyester acrylamide ester, polyester acrylate, methyl acrylate, ethyl acrylate, and one of monofunctional N-vinyl pyrrolidone, multifunctional polyethylene glycol dimethacrylate. The oligomer polyacrylamide ester is used as a diluent in the material system, and plays a role in reducing the viscosity of the material system.
The crosslinking type cracking agent is used as a main source for providing a dissolution fracture bond in material components, methacrylic anhydride is selected as a crosslinking agent of a photosensitive resin prepolymer, and optionally, N, N-methylene bisacrylamide is selected as a crosslinking agent for improving the forming precision in the high-precision forming process.
The macromolecular connecting agent comprises one of carboxymethyl cellulose, N-methyl pyrrolidone, polyvinylpyrrolidone, sodium polyacrylate, methyl cellulose, sodium carboxymethyl cellulose and sodium polyacrylate.
In order to improve the photosensitive effect and the photosensitive range of the photosensitive resin under different light machines, the cracking type free radical photoinitiator should contain one or more of acylphosphine oxides, alpha-hydroxyalkyl benzones and alpha-amine alkyl benzones, so as to meet the requirement of regulating and controlling the matching capacity of the photosensitive resin in the photosensitive range of 365 to 425nm by different component ratios.
Optionally, the photosensitive resin in the wavelength range of 365-385nm is compounded by selecting acylphosphine oxides and alpha-hydroxyalkyl benzophenone initiators, wherein the acylphosphine oxides at least comprise one of diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide and bis (2, 6-methoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide, and the alpha-hydroxyalkyl benzophenone at least comprises one of 2-hydroxy-2-methyl-1-phenyl-1-acetone and 1-hydroxycyclohexyl phenyl ketone.
Optionally, the photosensitive resin in the wavelength range of 385nm to 425nm is compounded by selecting acylphosphine oxide and alpha-amine alkyl benzophenone initiators, the acylphosphine oxide initiators are selected by the same expression as that in the above, and the alpha-amine alkyl benzophenone initiators comprise at least one of 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone and 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone.
The light-blocking agent at least comprises one of azo group or phenolic hydroxyl color-aiding group, and the light-blocking agent containing azo group chromophore at least selects one of phenylazo-2-naphthol, sodium p-dimethylaminoazobenzenesulfonate and methylene blue; optionally, the light-blocking agent containing the phenolic hydroxyl chromophore is at least one selected from the group consisting of phenylazo-2-naphthol, 1, 4-dihydroxyanthraquinone, 2-hydroxybenzophenone and 2, 6-dihydroxydibenzocyclohexanone. The azo group plays a role of chromophore in a photosensitive resin system to reduce the transmittance of ultraviolet light in the reaction process of the photoinitiator, and the chromophore group containing the phenolic hydroxyl group plays a role of the chromophore group in the photosensitive resin system to reduce the interaction rate of the photoinitiator and the active free radical in the photoinitiation reaction process.
Correspondingly, the invention provides a synthetic preparation method of soluble photosensitive resin suitable for high-precision 3D printing, the photosensitive resin has a wide response range and stable storage performance, the storage performance is embodied in that the photosensitive resin can be stored for one year without deterioration under a non-volatile and light-proof closed environment, the synthetic preparation process is simple, and the specific process refers to FIG. 8, and comprises the following steps:
(1) and (3) hermetically stirring the mixture of the polyacrylamide oligomer and the polymerization inhibitor in an anaerobic drying environment, and controlling the stirring time under different photosensitive resin compositions according to the characteristics and the content of the synthetic components of different prepolymers to obtain a preliminary crosslinked, clear and transparent prepolymer acrylamide material.
(2) Preheating the macromolecular connecting agent to 60-80 ℃ in a heating dish, grinding, adding the macromolecular connecting agent into the prepolymer while stirring, and uniformly mixing to obtain the first-stage composition with mechanical property and macromolecular crosslinking property.
(3) Selecting a light-resistant condition, keeping the stirring state, sequentially adding a light-resistant agent, a cracking type free radical photoinitiator and a crosslinking type cracking agent, keeping the temperature of the resin constant at 50-70 ℃, uniformly mixing until the color of the resin is clear and transparent, and hermetically storing the final product in a brown quartz vessel.
Preferably, the oxygen content of the prepolymer in the step one is reduced to below 1500ppm, the relative humidity is reduced to below 10%, or dry nitrogen or argon is introduced into a stirring environment.
Preferably, the environmental temperature in the first step is controlled to be kept at 45 to 65 ℃ under the condition of satisfying the composition and content characteristics of the prepolymer, the stirring speed in the heating environment cannot exceed 2000rpm in order to prevent implosion, and the stirring time is not less than 1 hour.
The stirring speed in the step (2) is 500-2500rpm, and the stirring time is 2-4 hours.
Preferably, the addition of the polymer connecting agent in the second step and the addition of the light-blocking agent in the third step need to be carried out from the position where the resin has the fastest stirring flow speed, so that the caking phenomenon caused by the excessively low dispersion speed is prevented; the addition of the photoinitiator in the third step should prevent the local self-polymerization phenomenon after the light-blocking agent is uniformly dispersed.
The stirring adopts a magnetic stirrer.
The heating adopts a constant temperature oil bath heating pan.
The obtained resin is stored in a brown quartz vessel in a sealed manner, and the water oxygen content in the use environment is strictly controlled, so that the validity period of the high-precision soluble resin is improved.
The high-precision soluble photosensitive resin can be stably used in a photocuring 3D printing process, and the storage time in a room temperature environment is about one year.
The soluble photosensitive resin prepared by the invention can be dissolved by using a dissolving solution after being molded, and the dissolving solution is an alkali solvent and at least one of solvents such as sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, ammonia water, sodium sulfide aqueous solution, triethylamine, triethylene diamine, n-butylamine and the like. Preferably, when the solubility of the aqueous solution in the selected alkaline solvent is 0.5 to 2mol/L, the dissolving effect is better, and the environmental compatibility of the aqueous solution dissolving agent is better than that of the organic solvent. Preferably, the selected organic solvent needs to be dissolved in a fume hood during the dissolving process, so as to prevent the organic solvent from volatilizing to pollute the environment.
The invention provides a processing method for inhibiting an interlayer grain effect after solidification, which reduces the offset of the interlayer grain along an ideal forming surface 2 to obtain an inhibition layer grain 3 shown in figure 1, and the method comprises the following specific steps:
(1) and (3) placing the solidified and formed part in an electrolytic fluorination liquid, soaking for 10-15 minutes, and removing the photosensitive resin remained on the surface to show the forming effect of the curved surface step after forming.
(2) Taking out the electronic fluoridizing liquid, cleaning the surface in deionized water, soaking in ethanol solution of sodium hydroxide, regulating soaking time according to the surface etching effect, taking out, and placing in the electronic fluoridizing liquid for cleaning.
(3) And (3) carrying out surface drying treatment on the treated molded part in a vacuum drying oven, controlling the treatment temperature to be 70-90 ℃, controlling the treatment time to be within 20 minutes, taking out and storing in a drying environment.
The solidified molded part needs to be soaked in electrolytic fluoride liquid or ethanol solution of sodium hydroxide, and the solution is not less than 20 times of the volume of the solidified part in the two soaking processes, so that the solidified molded part is completely soaked in the liquid for treatment.
In the step (1), at least one of FC-40, FMD-50 or FMD-120 with high evaporation speed and inert chemical property is selected as the electrolytic fluorinated liquid, and the surface of a large-area molded part is treated, and the surface can be treated by hydrofluoroether electronic fluorinated liquid.
In the step (2), the concentration of the sodium hydroxide alcoholic solution is controlled to be 0.1-0.25 mol/L, the dissolving temperature of the sodium hydroxide powder is controlled to be 60-80 ℃, and the concentration is selected according to the actual dissolving condition and the inhibition condition of surface striations.
The following description is made in conjunction with specific embodiments.
Example one
The embodiment is suitable for preparing materials sensitive to the forming precision of 150-200 um and the ultraviolet light of 365-385 nm.
Table 1 example one material composition of soluble photosensitive resin for high precision 3D printing
The preparation method based on the soluble photosensitive resin comprises the following steps:
(1) 35.7 parts of acrylic acid, 35 parts of hydroxymethyl acrylamide and 0.05 part of p-hydroxyanisole are added into a three-neck flask communicated with an inert dry atmosphere in sequence, and are stirred magnetically for 2 hours at the rotation speed of 500rpm at the mixing temperature of 60 ℃ and then are mixed uniformly to obtain the acrylic acid-acrylamide-based soluble photosensitive resin prepolymer (oligomer).
(2) Adding a high-molecular connecting agent into a quartz dish, raising the temperature to 70 ℃ in an inert atmosphere, adjusting the rotating speed of a prepolymer to 1500rpm, adding 10 parts of N-methylpyrrolidone preheated uniformly to the oligomer at 65 ℃, and magnetically stirring for 2 hours to obtain a mixture with uniform mixing and improved viscosity.
(3) Reducing the temperature of the synthesis environment to 50 ℃, carrying out light-shielding treatment on the synthesis environment, keeping the stirring speed of 1500rpm, sequentially adding 2 parts of 1, 4-dihydroxy anthraquinone, 4 parts of 2-hydroxybenzophenone, 1.5 parts of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide and 1.75 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone into the mixture, and stirring for 1 hour to obtain the uniformly mixed resin. And cooling to room temperature to obtain light brown viscous resin, transferring the resin to a brown bottle, keeping out of the sun, and sealing for storage to obtain the soluble photosensitive resin meeting the preparation requirements.
A method for inhibiting cured lamination of soluble photosensitive resin comprises the following steps:
(1) and (3) placing the cured and molded part into electrolytic fluorination liquid FC-50, and soaking for 10-15 minutes to remove the residual photosensitive resin on the surface.
(2) Taking out the electrolytic fluoridizing solution, cleaning the surface of the electrolytic fluoridizing solution in deionized water, soaking the electrolytic fluoridizing solution in 0.25mol/L sodium hydroxide ethanol solution for 20 minutes, and then placing the electrolytic fluoridizing solution in FC-50 for cleaning.
(3) And (3) drying in a vacuum drying oven, controlling the processing temperature at 70 ℃, processing for 15 minutes, taking out, and storing in a drying environment to obtain the high-precision 3D printed lamellar inhibiting microstructure component.
Example two
The embodiment is suitable for preparing materials sensitive to the molding precision of 150-200 um and the ultraviolet light of 385-425 nm.
Table 2 example two material compositions of high precision 3D printing soluble photosensitive resin
The preparation method based on the soluble photosensitive resin comprises the following steps:
(1) 35.7 parts of acrylic acid, 40 parts of dimethylacrylamide and 0.05 part of p-hydroxyanisole are added into a three-neck flask communicated with an inert dry atmosphere in sequence, and the mixture is uniformly mixed after being magnetically stirred for 2 hours at the rotating speed of 500rpm at the mixing temperature of 60 ℃ to obtain the acrylic acid-acrylamide-based soluble photosensitive resin prepolymer (oligomer).
(2) Adding a high-molecular connecting agent into a quartz dish, raising the temperature to 70 ℃ in an inert atmosphere, adjusting the rotating speed of a prepolymer to 1500rpm, adding 9.25 parts of N-methylpyrrolidone preheated uniformly to the oligomer at 65 ℃, and magnetically stirring for 2 hours to obtain a mixture with uniform mixing and improved viscosity.
(3) Reducing the temperature of the synthesis environment to 50 ℃, shading the synthesis environment, keeping the stirring speed of 1500rpm, sequentially adding 1.5 parts of 1, 4-dihydroxy anthraquinone, 1.5 parts of 2, 6-dihydroxy dibenzocyclohexanone, 1.5 parts of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide and 1.5 parts of 1-hydroxycyclohexyl phenyl ketone into the mixture, and stirring for 1 hour to obtain the uniformly mixed resin. And cooling to room temperature to obtain light brown viscous resin, transferring the resin to a brown bottle, keeping out of the sun, and sealing for storage to obtain the soluble photosensitive resin meeting the preparation requirements.
A method for inhibiting cured lamination of soluble photosensitive resin comprises the following steps:
(1) and (3) placing the cured and molded part into electrolytic fluorination liquid FC-50, and soaking for 10-15 minutes to remove the residual photosensitive resin on the surface.
(2) Taking out the electrolytic fluoridizing solution, cleaning the surface of the electrolytic fluoridizing solution in deionized water, soaking the electrolytic fluoridizing solution in 0.25mol/L sodium hydroxide ethanol solution for 20 minutes, and then placing the electrolytic fluoridizing solution in FC-50 for cleaning.
(3) And (3) drying in a vacuum drying oven, controlling the processing temperature at 70 ℃, processing for 15 minutes, taking out, and storing in a drying environment to obtain the high-precision 3D printed lamellar inhibition microstructure component, as shown in fig. 4 (a).
EXAMPLE III
The embodiment is suitable for preparing materials sensitive to the forming precision of 80-100 um and the ultraviolet light of 365-385 nm.
Table 3 material composition of soluble photosensitive resin for high precision 3D printing in example three
The preparation method based on the soluble photosensitive resin comprises the following steps:
(1) 35.5 parts of methacrylic acid, 35.5 parts of N, N-dimethylacrylamide and 0.05 part of hydroquinone are sequentially added into a three-neck flask communicated with an inert drying atmosphere, and the mixture is magnetically stirred for 2 hours at the rotating speed of 500rpm at the mixing temperature of 60 ℃ and then uniformly mixed to obtain the soluble photosensitive resin prepolymer (oligomer).
(2) Adding a high-molecular connecting agent into a quartz dish, raising the temperature to 70 ℃ in an inert atmosphere, adjusting the rotating speed of a prepolymer to 2000rpm, adding 12 parts of polyvinylpyrrolidone with uniform preheating temperature into an oligomer with the temperature of 65 ℃, and magnetically stirring for 2 hours to obtain a mixture with uniform mixing and improved viscosity.
(3) Reducing the temperature of the synthesis environment to 50 ℃, processing the synthesis environment in the dark, keeping the stirring speed of 2000rpm, sequentially adding 2 parts of 1, 4-dihydroxy anthraquinone, 2.4 parts of phenylazo-2-naphthol, 2 parts of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide and 1.75 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone into the mixture, and stirring for 1 hour to obtain the uniformly mixed resin. And cooling to room temperature to obtain light red viscous resin, transferring the resin to a brown bottle, keeping out of the sun, and sealing for storage to obtain the soluble photosensitive resin meeting the preparation requirements.
A method for inhibiting cured lamination of soluble photosensitive resin comprises the following steps:
(1) and (3) placing the cured and molded part in electrolytic fluorination liquid FC-120, and soaking for 10-15 minutes to remove the photosensitive resin remained on the surface.
(2) Taking out the electrolytic fluoridized solution, cleaning the surface of the electrolytic fluoridized solution in deionized water, soaking the electrolytic fluoridized solution in 0.25mol/L sodium hydroxide ethanol solution for 20 minutes, and then placing the electrolytic fluoridized solution in FC-120 for cleaning.
(3) And (3) drying in a vacuum drying oven, controlling the processing temperature at 70 ℃, processing for 15 minutes, taking out, and storing in a drying environment to obtain the high-precision 3D printed lamellar inhibiting microstructure component.
Example four
The embodiment is suitable for preparing materials sensitive to the molding precision of 80-100 um and the ultraviolet light of 385-425 nm.
Table 4 example four material compositions of high precision 3D printing soluble photosensitive resin
The preparation method based on the soluble photosensitive resin comprises the following steps:
(1) 37.3 parts of methacrylic acid, 36.45 parts of N, N-dimethylacrylamide and 0.05 part of hydroquinone are added into a three-neck flask communicated with an inert drying atmosphere in sequence, and are stirred magnetically for 2 hours at the rotating speed of 500rpm at the mixing temperature of 60 ℃ and then are mixed uniformly to obtain a soluble photosensitive resin prepolymer (oligomer).
(2) Adding a high-molecular connecting agent into a quartz dish, raising the temperature to 70 ℃ in an inert atmosphere, adjusting the rotating speed of a prepolymer to 2000rpm, adding 12 parts of polyvinylpyrrolidone with uniform preheating temperature into an oligomer with the temperature of 65 ℃, and magnetically stirring for 2 hours to obtain a mixture with uniform mixing and improved viscosity.
(3) Reducing the temperature of the synthesis environment to 50 ℃, shading the synthesis environment, keeping the stirring speed of 2000rpm, sequentially adding 1.8 parts of phenylazo-2-naphthol, 1.5 parts of 2-hydroxybenzophenone, 1.5 parts of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide and 1.5 parts of 1-hydroxycyclohexyl phenyl ketone into the mixture, and stirring for 1 hour to obtain the uniformly mixed resin.
(4) And cooling to room temperature to obtain light red viscous resin, transferring the resin to a brown bottle, keeping out of the sun, and sealing for storage to obtain the soluble photosensitive resin meeting the preparation requirements.
A method for inhibiting cured lamination of soluble photosensitive resin comprises the following steps:
(1) and (3) placing the cured and molded part in electrolytic fluorination liquid FC-120, and soaking for 10-15 minutes to remove the photosensitive resin remained on the surface.
(2) Taking out the electrolytic fluoridized solution, cleaning the surface of the electrolytic fluoridized solution in deionized water, soaking the electrolytic fluoridized solution in 0.25mol/L sodium hydroxide ethanol solution for 20 minutes, and then placing the electrolytic fluoridized solution in FC-120 for cleaning.
(3) And (3) drying in a vacuum drying oven, controlling the processing temperature at 70 ℃, processing for 15 minutes, taking out, and storing in a drying environment to obtain the high-precision 3D printed lamellar inhibition microstructure component, as shown in fig. 4 (b).
EXAMPLE five
The embodiment is suitable for preparing materials sensitive to the forming precision of 80-120 um and the ultraviolet light of 365-425 nm.
Table 5 example five material compositions of high precision 3D printing soluble photosensitive resin
The preparation method based on the soluble photosensitive resin comprises the following steps:
(1) 28 parts of methacrylic acid, 26 parts of N, N-dimethylacrylamide, 25.04 parts of N, N-methylenebisacrylamide and 0.05 part of hydroquinone are sequentially added into a three-neck flask communicated with an inert drying atmosphere, and the mixture is magnetically stirred for 2 hours at the mixing temperature of 60 ℃ at the rotating speed of 500rpm and then uniformly mixed to obtain a soluble photosensitive resin prepolymer (oligomer).
(2) Adding a high-molecular connecting agent into a quartz dish, raising the temperature to 70 ℃ in an inert atmosphere, adjusting the rotating speed of a prepolymer to 2000rpm, adding 9.5 parts of polyvinylpyrrolidone with uniform preheating temperature into oligomer with the temperature of 65 ℃, and magnetically stirring for 2 hours to obtain a mixture with uniform mixing and improved viscosity.
(3) The temperature of the synthesis environment was lowered to 50 ℃, the synthesis environment was protected from light, the stirring speed at 2000rpm was maintained, 1.2 parts of phenylazo-2-naphthol, 0.72 parts of 1, 4-dihydroxyanthraquinone, 0.54 parts of 2, 6-dihydroxydibenzocyclohexanone, 1.2 parts of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 1 part of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1 part of 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone were added to the mixture in this order, and after stirring for 1 hour, a uniformly mixed resin was obtained. And cooling to room temperature to obtain dark red viscous resin, transferring the resin to a brown bottle, keeping out of the sun, and sealing for storage to obtain the soluble photosensitive resin meeting the preparation requirements.
A method for inhibiting cured lamination of soluble photosensitive resin comprises the following steps:
(1) and (3) placing the cured and molded part in electrolytic fluorination liquid FC-120, and soaking for 10-15 minutes to remove the photosensitive resin remained on the surface.
(2) Taking out the electrolytic fluoridized solution, cleaning the surface of the electrolytic fluoridized solution in deionized water, soaking the electrolytic fluoridized solution in 0.25mol/L sodium hydroxide ethanol solution for 20 minutes, and then placing the electrolytic fluoridized solution in FC-120 for cleaning.
(3) And (3) drying in a vacuum drying oven, controlling the processing temperature at 70 ℃, processing for 15 minutes, taking out, and storing in a drying environment to obtain the high-precision 3D printed lamellar inhibition microstructure component, as shown in fig. 4 (c).
And (3) performance testing:
fig. 5 shows a light transmittance ratio and a high-precision insoluble ratio of two commercial resins of the material configured in the fifth embodiment of the present invention; in various embodiments, the shrinkage during curing and molding is related to the cracking agent in the material composition as shown in FIG. 6.
The molded article obtained in the fourth example was observed under a scanning electron microscope, and the effect comparison graph shown in fig. 7 was obtained by comparing the surface morphologies before and after the streak removal treatment. The present invention includes but is not limited to the embodiments described above, and any equivalent or partial modifications made under the spirit of the present invention are considered to be within the scope of the present invention.
Claims (10)
1. The soluble photosensitive resin is characterized by comprising, by mass, 70-80 parts of oligomer polyacrylamide ester, 5-10 parts of a crosslinking type cracking agent, 9-12 parts of a high-molecular linking agent, 3-5 parts of a cracking type free radical photoinitiator and 2-6 parts of a light-blocking agent for regulating and controlling molding precision.
2. The soluble photosensitive resin of claim 1, wherein the raw material further comprises 0.05 part of a polymerization inhibitor, the polymerization inhibitor being one of p-hydroxyanisole and hydroquinone.
3. The soluble photosensitive resin as claimed in claim 1, wherein said oligomer polyacrylamide ester is pre-polymerized with acrylic group and acrylamide group in any ratio, said acrylic group comprises at least one or more of acrylic acid, methacrylic acid, 2-ethacrylic acid, and 2-propylacrylic acid; the acrylamide group at least comprises one of acrylamide, hydroxymethyl acrylamide, dimethylacrylamide, N-dimethylacrylamide and N, N-methylene bisacrylamide;
the composition of the oligomer polyacrylamide ester also comprises synthesized oligomer comprising one of polyurethane acrylate, polyester acrylamide ester, polyester acrylate, methyl acrylate, ethyl acrylate, and monofunctional N-vinyl pyrrolidone, multifunctional polyethylene glycol dimethacrylate;
the crosslinking cracking agent at least comprises one of methacrylic anhydride and N, N-methylene bisacrylamide;
the high-molecular connecting agent comprises one of carboxymethyl cellulose, N-methyl pyrrolidone, polyvinylpyrrolidone, sodium polyacrylate, methyl cellulose, sodium carboxymethyl cellulose and sodium polyacrylate;
the cracking free radical photoinitiator contains one or more of acylphosphine oxides, alpha-hydroxyalkyl benzones and alpha-amine alkyl benzones, so that the matching capability of photosensitive resin in a photosensitive range of 365-425 nm can be regulated and controlled by different component ratios;
the light-blocking agent at least comprises one of azo group or phenolic hydroxyl color-aiding group, and the light-blocking agent containing azo group chromophore at least selects one of phenylazo-2-naphthol, sodium p-dimethylaminoazobenzenesulfonate and methylene blue; optionally, the light-blocking agent containing the phenolic hydroxyl chromophore is at least one selected from the group consisting of phenylazo-2-naphthol, 1, 4-dihydroxyanthraquinone, 2-hydroxybenzophenone and 2, 6-dihydroxydibenzocyclohexanone.
4. The soluble photosensitive resin of claim 3, wherein the photosensitive resin is prepared by combining acylphosphine oxide and α -hydroxyalkylphenone initiator selected from the group consisting of diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, bis (2, 6-methoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide, and α -hydroxyalkylphenone initiator selected from the group consisting of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxycyclohexylphenylketone, to provide a photosensitivity within the wavelength range of 365-385 nm.
5. The soluble photosensitive resin of claim 3, wherein the photosensitive resin is selected from acylphosphine oxides and α -aminoalkylphenone initiators to achieve a photosensitivity in the wavelength range of 385nm to 425nm, the acylphosphine oxides comprise at least one of diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, bis (2, 6-methoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide, and the α -aminoalkylphenone initiators comprise at least 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzylphenyl) butandine One of ketones.
6. The method for preparing the soluble photosensitive resin according to claim 3, comprising the steps of:
(1) in an anaerobic drying environment, hermetically stirring the mixture of the oligomer polyacrylamide ester and the polymerization inhibitor until a prepolymer liquid which is uniformly mixed and clarified is obtained;
(2) preheating a high-molecular connecting agent to 60-80 ℃ in a heating dish, grinding, adding the high-molecular connecting agent into the prepolymer while stirring, and uniformly mixing to obtain a first-stage composition with mechanical properties and high-molecular crosslinking properties;
(3) selecting a light-resistant condition, keeping the stirring state, sequentially adding a light-resistant agent, a cracking type free radical photoinitiator and a crosslinking type cracking agent, keeping the temperature of the resin constant at 50-70 ℃, uniformly mixing until the color of the resin is clear and transparent, and storing the resin product in a brown quartz vessel in a sealing manner.
7. The method according to claim 6, wherein the oxygen content in the anaerobic drying environment in step (1) is reduced to less than 1500ppm, the relative humidity is reduced to less than 10%, or dry nitrogen or argon is introduced into the stirring environment;
controlling the environmental temperature in the step (1) to be 45-65 ℃, wherein the stirring speed cannot exceed 2000rpm, and the stirring time is not less than 1 hour;
the stirring speed in the step (2) is 500-;
adding the high molecular connecting agent in the step (2) and adding the light-blocking agent in the step (3) need to be applied from the position with the fastest stirring flow speed;
in the step (3), the photoinitiator is added after the light-resisting agent is uniformly dispersed;
the stirring adopts a magnetic stirrer;
the heating adopts a constant temperature oil bath heating pan.
8. The method for suppressing the striations of a cured layer obtained by the method for preparing a soluble photosensitive resin according to claim 6, comprising the following steps:
(1) placing the cured and molded part in an electrolytic fluorination liquid, soaking for 10-15 minutes, and removing the photosensitive resin remained on the surface to show the molding effect of the curved surface step after molding;
(2) taking out the electronic fluoridizing liquid, cleaning the surface of the electronic fluoridizing liquid in deionized water, soaking the electronic fluoridizing liquid in an ethanol solution of sodium hydroxide, adjusting the soaking time according to the surface etching effect, taking out the electronic fluoridizing liquid, and placing the electronic fluoridizing liquid for cleaning;
(3) carrying out surface drying treatment on the treated molded part in a vacuum drying oven, controlling the treatment temperature to be 70-90 ℃, controlling the treatment time to be within 20 minutes, taking out and storing in a drying environment;
the solidified molded part needs to be soaked in electrolytic fluoride liquid or ethanol solution of sodium hydroxide, and the solution is not less than 20 times of the volume of the solidified part in the two soaking processes, so that the solidified molded part is completely soaked in the liquid for treatment.
9. The method according to claim 8, wherein the electrolytic fluorination liquid in step (1) is one of FC-40, FMD-50 or FMD-120, and the surface of the large-area molded part is treated by hydrofluoroether type electron fluorination liquid.
10. The method for suppressing striations of claim 8, wherein said alcoholic sodium hydroxide solution of step (2) is controlled to a concentration of 0.1 to 0.25mol/L and the dissolution temperature of the sodium hydroxide powder is controlled to a temperature of 60 to 80 ℃.
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