CN112111038B - Water-soluble photosensitive resin and preparation method and application thereof - Google Patents
Water-soluble photosensitive resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN112111038B CN112111038B CN202010803887.3A CN202010803887A CN112111038B CN 112111038 B CN112111038 B CN 112111038B CN 202010803887 A CN202010803887 A CN 202010803887A CN 112111038 B CN112111038 B CN 112111038B
- Authority
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- China
- Prior art keywords
- photosensitive resin
- resin composition
- compound
- printing
- diisocyanate
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 35
- 239000011347 resin Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000010146 3D printing Methods 0.000 claims abstract description 40
- 239000011342 resin composition Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000000016 photochemical curing Methods 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 14
- -1 ureido compound Chemical class 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000012948 isocyanate Substances 0.000 claims description 15
- 238000007639 printing Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 150000002513 isocyanates Chemical class 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical group COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 7
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-UHFFFAOYSA-N 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 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 5
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical group CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 4
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- KCWDJXPPZHMEIK-UHFFFAOYSA-N isocyanic acid;toluene Chemical class N=C=O.N=C=O.CC1=CC=CC=C1 KCWDJXPPZHMEIK-UHFFFAOYSA-N 0.000 claims description 4
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- 239000013638 trimer Substances 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- JJLDVMLIPANDEW-UHFFFAOYSA-N 2-ethyloctyl 4-(dimethylamino)benzoate Chemical compound CCCCCCC(CC)COC(=O)C1=CC=C(N(C)C)C=C1 JJLDVMLIPANDEW-UHFFFAOYSA-N 0.000 claims description 2
- 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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- NNAHKQUHXJHBIV-UHFFFAOYSA-N 2-methyl-1-(4-methylthiophen-2-yl)-2-morpholin-4-ylpropan-1-one Chemical compound CC1=CSC(C(=O)C(C)(C)N2CCOCC2)=C1 NNAHKQUHXJHBIV-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- AIXZBGVLNVRQSS-UHFFFAOYSA-N 5-tert-butyl-2-[5-(5-tert-butyl-1,3-benzoxazol-2-yl)thiophen-2-yl]-1,3-benzoxazole Chemical compound CC(C)(C)C1=CC=C2OC(C3=CC=C(S3)C=3OC4=CC=C(C=C4N=3)C(C)(C)C)=NC2=C1 AIXZBGVLNVRQSS-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 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
- 229930006711 bornane-2,3-dione Natural products 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- CCOSOBKLKCHGNO-UHFFFAOYSA-N ethoxy-(2,4,6-trimethylbenzoyl)phosphinic acid Chemical compound C(C)OP(O)(=O)C(C1=C(C=C(C=C1C)C)C)=O CCOSOBKLKCHGNO-UHFFFAOYSA-N 0.000 claims description 2
- YMCOIFVFCYKISC-UHFFFAOYSA-N ethoxy-[2-(2,4,6-trimethylbenzoyl)phenyl]phosphinic acid Chemical compound CCOP(O)(=O)c1ccccc1C(=O)c1c(C)cc(C)cc1C YMCOIFVFCYKISC-UHFFFAOYSA-N 0.000 claims description 2
- DUDCYUDPBRJVLG-UHFFFAOYSA-N ethoxyethane methyl 2-methylprop-2-enoate Chemical compound CCOCC.COC(=O)C(C)=C DUDCYUDPBRJVLG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 claims description 2
- 229920001427 mPEG Polymers 0.000 claims description 2
- 239000006224 matting agent Substances 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 2
- 229940099373 sudan iii Drugs 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 2
- FHNINJWBTRXEBC-UHFFFAOYSA-N Sudan III Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 FHNINJWBTRXEBC-UHFFFAOYSA-N 0.000 claims 1
- 125000006309 butyl amino group Chemical group 0.000 claims 1
- UIYIJRAZCUWXTG-UHFFFAOYSA-N n',n'-ditert-butylethane-1,2-diamine Chemical compound CC(C)(C)N(C(C)(C)C)CCN UIYIJRAZCUWXTG-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 3
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 17
- 238000012360 testing method Methods 0.000 description 12
- 238000001723 curing Methods 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 229940125904 compound 1 Drugs 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical group CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000012815 thermoplastic material Substances 0.000 description 2
- 239000004634 thermosetting polymer Substances 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000005184 irreversible process Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JYXKYKIDIKVWNY-UHFFFAOYSA-N n'-tert-butylethane-1,2-diamine Chemical compound CC(C)(C)NCCN JYXKYKIDIKVWNY-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FHNINJWBTRXEBC-HXEHWPEMSA-N sudan iii Chemical compound OC1=CC=C2C=CC=CC2=C1\N=N\C(C=C1)=CC=C1\N=N/C1=CC=CC=C1 FHNINJWBTRXEBC-HXEHWPEMSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 125000006318 tert-butyl amino group Chemical group [H]N(*)C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
- C07C273/1818—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety from -N=C=O and XNR'R"
- C07C273/1827—X being H
-
- 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
-
- 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
-
- 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
-
- 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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a photosensitive resin composition and a preparation method and application thereof, belonging to the field of intelligent high polymer materials. The photosensitive resin is prepared from a carbamido compound, a monomer, a photoinitiator, a flatting agent and a flatting agent in a light-proof environment. The water-soluble printed piece formed by photocuring 3D printing can be dissolved in pure water or aqueous solution pieces and can be used as a sacrificial mold, so that materials which cannot be directly printed can also construct a three-dimensional structure product in this way.
Description
Technical Field
The invention relates to a water-soluble photosensitive resin and a preparation method and application thereof, belonging to the field of high polymer materials.
Background
The photocuring 3D printing technology has the advantages of short manufacturing period, high forming precision, capability of being customized and the like, is widely applied to the fields of aerospace, industry, medical treatment and the like, and the type and the performance of a 3D printing material determine the development and the application of the photocuring 3D printing technology. The photocuring 3D printing material generally needs to be rapidly cured to form a required part under the irradiation of ultraviolet light, because most of the photocuring 3D printing material is unsaturated resin, and under the irradiation of ultraviolet light with a certain wavelength, a photoinitiator absorbs light energy, and electrons are transited from a ground state to an excited state to form active free radicals or cations. Under the action of active free radicals or cations, molecular chains containing unsaturated functional groups (mainly C ═ C bonds) are polymerized to form a crosslinked network polymer, and the formed network polymer is thermosetting polymerization and often only shows swelling in water or a solvent and cannot be dissolved.
Only a few parts of photosensitive materials can be used directly for photocuring 3D printing at present. Conventional processing methods, such as injection molding, cannot build complex three-dimensional hollow structures because of the difficulty in demolding. Secondly, some photosensitive resins need to be endowed with conductivity, conductive materials such as carbon black, graphene and carbon nanotubes are often added into the materials, on one hand, the photosensitive viscosity is increased rapidly due to the fact that a large amount of conductive materials are added, the requirement for the leveling property in the 3D printing process cannot be met, on the other hand, the conductive materials are black substances and have strong extinction property, and the large amount of conductive materials are low in curing depth and difficult to form. Moreover, most of the monomers and oligomers have toxicity and irritation to eyes and skin, and the printed materials cannot meet the application in the biological field.
In order to enable some high polymer materials which cannot be subjected to photocuring 3D printing to also construct a complex hollowed-out structure, R.Liska et al introduces an indirect 3D printing method, a mold is printed out through a photocuring 3D printer, then non-printed two-component silicone rubber is injected into the mold, the mold is cured at room temperature for a period of time, and then the mold is immersed in a sodium hydroxide solution with the concentration of 1 mol per liter for a period of time, and the printed mold is dissolved, so that silicone rubber with a three-dimensional structure is remained. However, such photosensitive resins require dissolution with lye, which can decompose some of the cast materials, such as ester group-containing polymeric materials, and are not suitable for large-scale applications. Shihong Deng et al use a printing with a line light to print thermoplastic materials that are soluble in hot water, but which are thermoplastic materials that tend to swell with water, making the mold dimensionally unstable and not easily stable for long periods of time, and secondly because the printed material is thermoplastic, no crosslinked network is formed and the surface dissolves in the monomer during printing, resulting in some details not being revealed.
Disclosure of Invention
In order to improve the technical problem, the invention provides a photosensitive resin composition, which comprises a carbamido compound, a monomer, a photoinitiator, a flatting agent and a leveling agent.
According to an embodiment of the present invention, the photosensitive resin composition comprises the following components in parts by weight: 1-50 parts of carbamido compound, 10-98 parts of monomer, 0.3-15 parts of photoinitiator, 0.02-0.5 part of flatting agent and 0.02-3 parts of flatting agent.
According to the technical scheme of the invention, the carbamido compound is obtained by reacting a tert-butyl amino compound with isocyanate.
According to an embodiment of the present invention, the method for preparing the ureido compound comprises the steps of:
mixing and reacting a tert-butylamino compound and isocyanate to obtain a ureido compound, and adding a polymerization inhibitor after the reaction is finished.
According to an embodiment of the present invention, the tert-butylamino compound is selected from at least one of ethyl 2- (tert-butylamino) methacrylate, N-bis (tert-butyl) ethylenediamine;
according to an embodiment of the present invention, the isocyanate is selected from at least one of diphenylmethane diisocyanate, isocyanoethyl methacrylate, toluene diisocyanate, hydrogenated phenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate trimer;
according to an embodiment of the present invention, the polymerization inhibitor may be hydroxyanisole;
according to an embodiment of the invention, the molar ratio of polymerization inhibitor to isocyanate is 0.02 to 0.12:100, such as 0.04 to 0.1:100, exemplary 0.08: 100;
according to an embodiment of the invention, the molar ratio of tert-butylamino groups in the tert-butylamino compound to isocyanate groups in the isocyanate is 1:0.8-1.2, for example 1: 1;
according to an embodiment of the invention, the reaction time is 0.1 to 5h, such as 0.1 to 2h, exemplary 0.5h, 1h, 1.5 h;
according to an embodiment of the invention, the temperature of the reaction is between 0 and 50 ℃, such as between 10 and 40 ℃.
By way of example, the ureido compound is prepared by the following method:
and (2) reacting the ethyl 2- (tert-butylamino) methacrylate with isophorone diisocyanate and other functional groups at 0-50 ℃ for 0.1-2 h, adding a polymerization inhibitor p-hydroxyanisole, and uniformly stirring to obtain the ureido compound.
According to the technical scheme of the invention, the ureido compound is formed by 2- (tert-butylamino) ethyl methacrylate and the following isocyanate compounds: selected from diphenylmethane diisocyanate, isocyano ethyl methacrylate, toluene diisocyanate, hydrogenated phenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate trimer.
According to the technical scheme of the invention, the carbamido compound is formed by N, N-bis (tert-butyl) ethylene diamine and the following isocyanate compound: selected from diphenylmethane diisocyanate, isocyano ethyl methacrylate, toluene diisocyanate, hydrogenated phenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate trimer.
According to a preferred embodiment of the invention, the ureido compound is selected from the following compounds:
according to an embodiment of the invention, the monomer is a monofunctional compound selected from at least one of N, N-dimethylacrylamide, 4-acryloylmorpholine, methacrylamide, acrylamide, N-vinylpyrrolidone, methacrylic acid, N-methylolacrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, poly (ethylene glycol) methyl ether methacrylate and dimethylaminoethyl methacrylate.
According to an embodiment of the invention, the photoinitiator is a free radical initiator selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenylphosphorus oxide, 2,4, 6-trimethylbenzoyl-ethoxy-phenylphosphorus oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphorus oxide, ethyl 2,4, 6-trimethylbenzoylphosphonate, 2-dimethoxy-1, 2-diphenylethanone, 2-ethyloctyl-4-dimethylaminobenzoate, ethyl 4-dimethylamino-benzoate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, and mixtures thereof, At least one of ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, camphorquinone and ethyl 4-dimethylaminobenzoate.
According to an embodiment of the invention, the matting agent is selected from at least one of sudan i, sudan iii, basf-orexin orange, optical brightener OB.
The kind of the leveling agent in the present invention is not particularly limited, and commercially available leveling agents known in the art may be selected, for example, one or a combination of two or more selected from BYK-302, BYK-358N, BYK-361N, BYK-310 and BYK-3550 of Bick, Germany, and one or a combination of two or more selected from TEGO wet500, TEGO 450, TEGO 410, TEGO 432, TEGO KL245, TEGO 710, TEGO 700 and TEGO 655 of Digao; the leveling agent can reduce the surface tension of the resin, improve the fluidity of the resin and further improve the printing precision;
the invention also provides a preparation method of the photosensitive resin, which comprises the following steps:
under the condition of keeping out of the sun, mixing a carbamido compound, a monomer, a photoinitiator, a flatting agent and a flatting agent to obtain the photosensitive resin composition;
as an example, the photosensitive resin was prepared by the following method:
pouring the carbamido compound, the monomer, the photoinitiator, the flatting agent and the flatting agent into a container, stirring at a high speed for 0.2-1 h at 40-60 ℃, activating the flatting agent to enable the photoinitiator to be completely dissolved and dispersed in the resin solution, and finally stirring for 0.1-0.3 h by a planetary stirrer with vacuumizing to obtain the photosensitive resin composition.
The invention also provides application of the photosensitive resin composition, which is used in the technical field of photocuring 3D printing.
The invention also provides application of the photosensitive resin composition in photocuring 3D printing, which is characterized by being applied to photocuring Stereolithography (SLA), digital projection processing (DLP), desktop Liquid Crystal (LCD) printing, Continuous Liquid Interface (CLIP), two-photon 3D printers and multi-material 3D printing.
The use according to the present invention, wherein the photosensitive resin composition is used for photocuring water-soluble prints for 3D printing.
The use according to the present invention, wherein the photosensitive resin composition is used for photocuring a water-soluble support material for 3D printing.
The product prepared by the photosensitive resin composition through photocuring 3D printing can be dissolved in pure water or aqueous solution and used as a sacrificial mold, so that materials which cannot be directly printed can also construct a three-dimensional structure product in such a way.
According to an embodiment of the invention, the use comprises injecting a casting material into the water-soluble photo-cured 3D printed article, after the casting material is shaped, dissolving the water-soluble photo-cured 3D printed article with an aqueous solution to obtain a cast shaped material.
In the present invention, the "photosensitive resin" contains an ureido compound, the urea bond of which is substituted with a bulky t-butyl group, so that the urea bond becomes unstable and reversibly dissociates into isocyanate and amine. Isocyanates can hydrolyze in aqueous solution to form amines and carbon dioxide, which is an irreversible process, changing the equilibrium favours the dissociation reaction of the ureido compounds, ultimately leading to irreversible complete degradation of the ureido compounds.
The 'water-soluble printing piece' has certain mechanical strength and hardness, and meets the injection pressure of a casting material.
The "water-soluble print" in the present invention means a material that dissolves in water or an aqueous solution at room temperature or under heating.
Advantageous effects
(1) The photo-curing 3D printing photosensitive resin composition provided by the invention is printed to form a thermosetting polymer, the thermosetting polymer is not easy to dissolve in a monomer in the printing process, the details of a printed part can be well embodied, and after post-curing, the photo-curing 3D printing photosensitive resin composition has strong stability, is not easy to absorb water and expand, and can be suitable for common photo-curing 3D printers in the market.
(2) The water-soluble printing piece formed by 3D printing of the photosensitive resin composition can be directly dissolved in distilled water or aqueous solution, and the dissolving condition is mild. When the sacrificial mold is used as a sacrificial mold, the damage to poured materials is small, and the poured materials cannot be corroded by alkali or acid. Meanwhile, the hollow printing piece has better strength and hardness, and can support the pressure of material casting when other materials are poured into the hollow printing piece, particularly when the materials are injected by vacuum pumping. Also has better temperature resistance, and can not deform when used at medium and low temperature (40-90 ℃).
(3) The photosensitive resin composition can also be used as a water-soluble support material, particularly for a micro printer, when some microstructures are printed, the support cannot be mechanically removed, and the water-soluble support material can meet the printing requirements of some microstructures.
Drawings
FIG. 1(a) is a nuclear magnetic spectrum of ureido compound 1 prepared in example 1 of the present invention (deuterated reagent used for detection is deuterated dimethyl sulfoxide); (b) is the mass spectrum of the ureido compound 1 prepared in example 1 (the solvent used for detection is acetonitrile, and the sodium cation mode is adopted);
FIG. 2 is a graph of viscosity versus shear rate for a photosensitive resin prepared in example 1 of the present invention;
FIG. 3 is a digital photograph of a hollow print prepared in example 1 of the present invention;
FIG. 4 is a digital photograph of a process of printing a dissolution;
figure 5 digital photographs of a thermoplastic print and the print of example 1.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
1. The preparation of the ureido compound 1 comprises the following specific steps:
at room temperature, mixing 25.02g of diphenylmethane diisocyanate and 37.04g of 2- (tert-butylamino) ethyl methacrylate, reacting for 0.5h, taking out a small amount of sample, detecting that the characteristic peak of-NCO completely disappears by infrared to show that the diphenylmethane diisocyanate has completely reacted, adding 0.01g of hydroxyanisole into the reaction system, and stirring uniformly to obtain the ureido compound 1, MS M/z (ESI):643.34[ M +23], wherein the attached figure 1 is a nuclear magnetic spectrum and a mass spectrum of the ureido compound 1.
2. The process for preparing photosensitive resin by using the ureido compound 1 and photocuring 3D printing is as follows:
carbamido compound 1(5g), 4-acryloyl morpholine (95g), 2,4, 6-trimethylbenzoyl-ethoxy-phenyl phosphorus oxide (2.5g), bosfu orili orange (0.25g) and BYK-302(0.25g) were weighed in a beaker, stirred at 40 ℃ for 20min using a high-speed homogenizer, and finally stirred with a vacuum planetary stirrer for 10min to obtain a clear liquid, and the obtained liquid (photosensitive resin) was put into a Digital Light Processing (DLP)3D printer for 3D printing molding. And cleaning the printed 3D printing piece with isopropanol, and curing for 10min in an ultraviolet curing box.
The post-cured print was immersed in water and the print was observed for dissolution at 40 c, as shown in figure 4.
The photo-curing 3D printing resin in this example was subjected to performance tests, and the test results are shown in table 1.
1. The results of the viscosity measurements of the photosensitive resin according to GB/T21059-2007, (viscosity measured at 25 ℃ at different shear rates) are shown in FIG. 1, and it can be seen from the graph of FIG. 2 that it is a Newtonian fluid with a viscosity of about 50.5 mPa.s.
2. Modulus of rupture and tensile strength test: the photosensitive resin prepared in the embodiment is printed with a standard sample strip required by GB/T1040.1-2018 by a photocuring 3D printer, and the modulus and the tensile strength of the standard sample strip are tested according to GB/T1040.1-2018.
Fig. 3 is a picture of a hollow square printed by the photosensitive resin of the embodiment through a DLP3D printer.
Fig. 4 is a picture of a 3D print soaked in water at 40 ℃ for 7 hours.
Example 2
1. The preparation of the ureido compound 2 comprises the following specific steps:
22.2g of isophorone diisocyanate and 37.04g of 2- (tert-butylamino) ethyl methacrylate are mixed at room temperature, after 0.5h of reaction, a small amount of sample is taken out, the characteristic peak of-NCO by infrared detection is completely disappeared to show that isophorone diisocyanate is completely reacted, 0.01g of hydroxyanisole is added into the reaction system, and after uniform stirring, ureido compound 2 is obtained, MS M/z (ESI) 615.42[ M +23 ].
2. The process for preparing photosensitive resin by using the ureido compound 2 and photocuring 3D printing is as follows:
the ureido compound 2(30g), N-dimethylacrylamide (70g), 2,4, 6-trimethylbenzoyl-ethoxy-phenyl phosphorus oxide (2.5g), Sudan I (0.25g) and BYK-302(0.25g) are weighed in a beaker, stirred for 20min at 40 ℃ by using a high-speed homogenizer, and finally stirred for 10min by using a vacuum planetary stirrer to remove bubbles to obtain clear liquid, and the obtained liquid (photosensitive resin) is put into a Digital Light Processing (DLP)3D printer for 3D printing and molding. And cleaning the printed 3D printing piece with isopropanol, and curing for 10min in an ultraviolet curing box.
The photocured 3D-printed sample strips and the resin in this example were subjected to performance testing in the same test method as in example 1, and the test results are shown in table 1.
Example 3
3. The preparation of the ureido compound 3 comprises the following specific steps:
16.0g of p-phenylene diisocyanate and 37.04g of 2- (tert-butylamino) ethyl methacrylate were mixed at room temperature, and after 0.5 hour of reaction, a small amount of sample was taken out, and the characteristic peak of-NCO by infrared detection was completely disappeared to show that p-phenylene diisocyanate had completely reacted, 0.01g of hydroxyanisole was added to the reaction system, and after stirring well, ureido compound 3, MS M/z (ESI):553.31[ M +23], was obtained.
2. The process for preparing photosensitive resin by using the ureido compound 3 and photocuring 3D printing is as follows:
carbamido compound 3(15g), N-vinyl pyrrolidone (85g), bis (2,4, 6-trimethylbenzoyl) -phenyl phosphorus oxide (2.5g), Sudan I (0.25g) and BYK-302(0.25g) are weighed in a beaker, stirred for 30min at 40 ℃ by using a high-speed homogenizer, and finally stirred for 10min by using a vacuum planetary stirrer to remove bubbles to obtain clear liquid, and the obtained liquid (photosensitive resin) is put into a Digital Light Processing (DLP)3D printer for 3D printing and molding. And cleaning the printed 3D printing piece with isopropanol, and curing for 10min in an ultraviolet curing box.
The photocured 3D-printed sample strips and the resin in this example were subjected to performance testing in the same test method as in example 1, and the test results are shown in table 1.
Example 4
1. The preparation of the ureido compound 4 comprises the following specific steps:
at room temperature, 16.8g of hexamethylene diisocyanate and 37.04g of 2- (tert-butylamino) ethyl methacrylate were mixed, and after 0.5 hour of reaction, a small amount of sample was taken out, the characteristic peak of-NCO by infrared detection was completely disappeared to show that p-phenylene diisocyanate had completely reacted, 0.01g of hydroxyanisole was added to the reaction system, and after stirring well, ureido compound 4, MS M/z (ESI):561.37[ M +23], was obtained.
2. The process for preparing photosensitive resin by using the ureido compound 4 and photocuring 3D printing is as follows:
the ureido compound 4(20g), methacrylic acid (80g), bis (2,4, 6-trimethylbenzoyl) -phenyl phosphorus oxide (2.5g), Sudan I (0.25g) and BYK-302(0.25g) are weighed in a beaker, stirred for 30min at 40 ℃ by using a high-speed homogenizer, and finally stirred for 10min by using a vacuum planetary stirrer to remove bubbles to obtain clear liquid, and the obtained liquid (photosensitive resin) is put into a Digital Light Processing (DLP)3D printer for 3D printing and molding. And cleaning the printed 3D printing piece with isopropanol, and curing for 10min in an ultraviolet curing box.
The photocured 3D-printed sample strips and the resin in this example were subjected to performance testing in the same test method as in example 1, and the test results are shown in table 1.
Example 5
1. The preparation of the ureido compound 5 comprises the following specific steps:
31g of isocyano ethyl methacrylate and 17.2g of 17.2g N, N-bis (tert-butyl) ethylene diamine were mixed at room temperature, and after 0.5 hour of reaction, a small amount of sample was taken out, and the peak of-NCO characteristics was completely disappeared by infrared detection, indicating that p-phenylene diisocyanate had completely reacted, 0.01g of hydroxyanisole was added to the reaction system, and after stirring uniformly, ureido compound 5, MS M/z (ESI):505.31[ M +23] was obtained.
2. The process for preparing photosensitive resin by using the ureido compound 5 and photocuring 3D printing is as follows:
5(20g) of ureido compound, 30g of methacrylic acid, 50g of 4-acryloyl morpholine, 2.5g of bis (2,4, 6-trimethylbenzoyl) -phenyl phosphorus oxide, 0.25g of Sudan I and 0.25g of BYK-302 were weighed in a beaker, stirred at 40 ℃ for 30min by using a high-speed homogenizer, and finally stirred by a vacuum planetary stirrer for 10min to remove bubbles to obtain a clear liquid, and the obtained liquid (photosensitive resin) was put into a Digital Light Processing (DLP)3D printer for 3D printing and molding. And cleaning the printed 3D printing piece with isopropanol, and curing for 10min in an ultraviolet curing box.
The photocured 3D-printed sample strips and the resin in this example were subjected to performance testing in the same test method as in example 1, and the test results are shown in table 1.
Table 1 results of performance testing of articles prepared in examples 1-5
The viscosity test in table 1 was performed on a photosensitive resin, and the tensile strength, tensile modulus, and shore (D) hardness were measured on the print.
Comparative example 1:
weighing 4-acryloyl morpholine (100g), 2,4, 6-trimethylbenzoyl-ethoxy-phenyl phosphorus oxide (2.5g), bosoft orizanol orange (0.25g) and BYK-302(0.25g) in a beaker, stirring for 20min at 40 ℃ by using a high-speed homogenizer, finally stirring for removing bubbles for 10min by using a vacuum planetary stirrer to obtain clear liquid, putting the obtained liquid (photosensitive resin) into a Digital Light Processing (DLP)3D printer, and carrying out 3D printing molding to obtain a thermoplastic printing part. Fig. 5 is a comparison of a comparative example 1 thermoplastic print with a print of example 1. Whereas the thermoplastic print partially dissolved during printing and some details were not visible like the eye of the print, example 1 formed a thermoset polymer and was not soluble during printing and some details were clearly visible.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (17)
1. A photosensitive resin composition comprises a carbamido compound, a monomer, a photoinitiator, a flatting agent and a flatting agent;
the ureido compound is prepared by the following method:
mixing a tert-butylamino compound and isocyanate for reaction to obtain a ureido compound, and adding a polymerization inhibitor after the reaction is finished;
when the tert-butylamino compound is 2- (tert-butylamino) ethyl methacrylate; the isocyanate is selected from at least one of diphenylmethane diisocyanate, toluene diisocyanate, hydrogenated phenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, naphthalene diisocyanate and hexamethylene diisocyanate trimer;
when the tert-butylamino compound is N, N-bis (tert-butyl) ethylenediamine, the isocyanate is isocyanoethyl methacrylate;
the molar ratio of the tertiary butyl amino group in the tertiary butyl amino compound to the isocyanate group in the isocyanate is 1: 0.8-1.2.
2. The photosensitive resin composition according to claim 1, wherein the polymerization inhibitor is hydroxyanisole.
3. The photosensitive resin composition according to claim 1, wherein the urea-based compound is selected from the group consisting of:
4. the composition according to any one of claims 1 to 3, wherein the photosensitive resin composition comprises the following components in parts by weight: 1-50 parts of carbamido compound, 10-98 parts of monomer, 0.3-15 parts of photoinitiator, 0.02-0.5 part of flatting agent and 0.02-3 parts of flatting agent.
5. The photosensitive resin composition according to claim 1 or 2, wherein the molar ratio of the polymerization inhibitor to the isocyanate is 0.02 to 0.12: 100;
the reaction time is 0.1-5 h;
the temperature of the reaction is 0-50 ℃.
6. The photosensitive resin composition according to claim 1 or 2, wherein the molar ratio of the polymerization inhibitor to the isocyanate is 0.04-0.1: 100;
the reaction time is 0.1-2 h;
the temperature of the reaction is 10-40 ℃.
7. The photosensitive resin composition according to claim 1 or 2, wherein the urea-based compound is prepared by a method comprising:
and (2) reacting the ethyl 2- (tert-butylamino) methacrylate with isophorone diisocyanate and other functional groups at 0-50 ℃ for 0.1-2 h, adding a polymerization inhibitor p-hydroxyanisole, and uniformly stirring to obtain the ureido compound.
8. The photosensitive resin composition according to any one of claims 1 to 3, wherein the monomer is a monofunctional compound selected from at least one of N, N-dimethylacrylamide, 4-acryloylmorpholine, methacrylamide, acrylamide, N-vinylpyrrolidone, methacrylic acid, N-methylolacrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, poly (ethylene glycol) methyl ether methacrylate and dimethylaminoethyl methacrylate.
9. The photosensitive resin composition according to any one of claims 1 to 3, wherein the photoinitiator is a radical initiator selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenylphosphorus oxide, 2,4, 6-trimethylbenzoyl-ethoxy-phenylphosphorus oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphorus oxide, ethyl 2,4, 6-trimethylbenzoylphosphonate, 2-dimethoxy-1, 2-diphenylethanone, 2-ethyloctyl-4-dimethylaminobenzoate, ethyl 4-dimethylamino-benzoate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and mixtures thereof, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, 2,4, 6-trimethylbenzoylphenylphosphonic acid ethyl ester, camphorquinone, and 4-dimethylaminobenzoic acid ethyl ester.
10. The photosensitive resin composition according to any one of claims 1 to 3, wherein the matting agent is at least one selected from Sudan I, Sudan III, Pasteur orange, and optical brightener OB.
11. The photosensitive resin composition as claimed in any one of claims 1 to 3, wherein the leveling agent is selected from one or a combination of two or more of BYK-302, BYK-358N, BYK-361N, BYK-310 and BYK-3550 from Bick, Germany, and at least one of TEGO wet500, TEGO 450, TEGO 410, TEGO 432, TEGO KL245, TEGO 710, TEGO 700 and TEGO 655 from Digao.
12. A method for preparing the photosensitive resin composition of any one of claims 1 to 11, comprising the steps of:
and mixing the carbamido compound, the monomer, the photoinitiator, the flatting agent and the flatting agent under the condition of keeping out of the sun to obtain the photosensitive resin composition.
13. The method of claim 12, comprising the steps of:
pouring the carbamido compound, the monomer, the photoinitiator, the flatting agent and the flatting agent into a container, stirring at a high speed for 0.2-1 h at 40-60 ℃, activating the flatting agent to enable the photoinitiator to be dissolved and dispersed in the resin solution, and finally vacuumizing and stirring for 0.1-0.3 h to obtain the photosensitive resin composition.
14. Use of the photosensitive resin composition of any one of claims 1 to 11 in photocuring 3D printing.
15. Use according to claim 14, in stereolithography, digital projection processing, desktop-level liquid crystal printing, continuous liquid interface, two-photon 3D printer or multi-material 3D printing.
16. Use according to claim 14, wherein the photosensitive resin composition is used for photocuring water-soluble prints for 3D printing.
17. Use according to claim 14, wherein the photosensitive resin composition is used for photocuring water-soluble support materials for 3D printing.
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| JP4488936B2 (en) * | 2005-03-14 | 2010-06-23 | 三洋化成工業株式会社 | Active energy ray-curable coating composition |
| CN108139665A (en) * | 2015-12-22 | 2018-06-08 | 卡本有限公司 | For with the dual precursor resin system of the increasing material manufacturing of dual cure resin |
| CN108359053A (en) * | 2018-02-01 | 2018-08-03 | 中国科学院福建物质结构研究所 | A kind of compositions of ultraviolet curing type and its preparation method and application |
| CN110358020A (en) * | 2019-08-26 | 2019-10-22 | 江西迈亚科技有限公司 | A kind of photosensitive resin and a kind of method of 3D printing polyureas |
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