CN107936146A - For 3D printing technique by visible light-initiated photoinitiator composite and application - Google Patents
For 3D printing technique by visible light-initiated photoinitiator composite and application Download PDFInfo
- Publication number
- CN107936146A CN107936146A CN201710698646.5A CN201710698646A CN107936146A CN 107936146 A CN107936146 A CN 107936146A CN 201710698646 A CN201710698646 A CN 201710698646A CN 107936146 A CN107936146 A CN 107936146A
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- China
- Prior art keywords
- photoinitiator
- acrylate
- photo
- light source
- visible light
- Prior art date
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- 238000010146 3D printing Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 34
- 238000000016 photochemical curing Methods 0.000 claims abstract description 26
- -1 sulphur salt compounds Chemical class 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 230000003993 interaction Effects 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 claims description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920005906 polyester polyol Polymers 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 238000000904 thermoluminescence Methods 0.000 claims description 3
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- LJRSZGKUUZPHEB-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxypropoxy)propoxy]propyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COC(C)COC(=O)C=C LJRSZGKUUZPHEB-UHFFFAOYSA-N 0.000 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000007859 condensation product Substances 0.000 claims description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims 1
- 125000005410 aryl sulfonium group Chemical group 0.000 claims 1
- 125000004386 diacrylate group Chemical group 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 claims 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 2
- 238000001723 curing Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 0 *c(cc(C(C1C(O2)=C(*)C3OC3C(*)=C1)c1c(*)c(*)c(*)c(*)c1*)c2c1*)c1O Chemical compound *c(cc(C(C1C(O2)=C(*)C3OC3C(*)=C1)c1c(*)c(*)c(*)c(*)c1*)c2c1*)c1O 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical class C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-(1,1-dimethylethyl)-phenol Natural products CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 238000007630 basic procedure Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005520 diaryliodonium group Chemical group 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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
- 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
-
- 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
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
The present invention provide it is a kind of it is new be used for 3D printing technique by visible light-initiated photoinitiator composite, it is by key light initiator and helps photoinitiator to form, wherein key light initiator and to help the weight ratio of photoinitiator be 1:0.1 10, preferably 1:0.2‑2；Wherein described key light initiator is iodine salt compounds, sulphur salt compounds or their any mixture；It is described to help shown in the structural formula such as formula (I) of photoinitiator：In formula (I), R is selected from H, Cl, Br, I, NO2In one or more, M is selected from H, Na, K, Li, NH4In one or more.The photoinitiator composite is suitable for the photo-curing material used in photocuring 3D printing forming technique, can be excited by visible light source so as to trigger the rapid curing molding of material, have the advantages that efficiency of initiation is high, stability is good, and security performance is high.
Description
Technical field
The present invention relates to field of material engineering technology, specifically, be related to it is a kind of for 3D printing technique by visible ray
The photoinitiator composite of initiation and application.
Background technology
A kind of emerging technology of 3D (three-dimensional) printing techniques as rapid shaping field, is referred to as " having industrial revolution meaning
The manufacturing technology of justice ".The main flow produced with the technology is：First appliance computer Software for Design goes out the processing of solid
Pattern, then (is commonly called as " 3D printer ") by specific former, is successively increased with the solid material of liquefaction, powdered etc.
Material generates product.It is different from traditional removal materials processing technology, therefore also known as addition manufacture, also referred to as increasing material manufacturing
Or increment manufacture.
3D printing manufacturing process flow is short, it is full-automatic, can be achieved making in site, manufacture more rapidly, it is more efficient.It is three-dimensional
The object of structure first resolves into two-dimensional layered structure, and successively adding up forms three-dimensional article.Therefore, 3D printing technique can be with principle
Produce any complicated structure." from below to up " accumulation mode for realize it is non-it is even cause material, functionally gradient device more
It is advantageous.Difficult molding component disposably can directly be manufactured by " printing " mode, it is not necessary to by assembling splicing etc.
Complex process is realized.
At present, the main technique of 3D printing has optical soliton interaction, material injection, bonding agent injection, Fused Deposition Modeling, choosing
Selecting property is laser sintered, piece is laminated, oriented energy deposits etc..Wherein photocuring 3D printing forming technique is a kind of using extensive
3D printing technique.Its basic procedure is that photosensitive resin is ejected by 3D printer nozzle bore, and light source is scanned in resin surface
Afterwards, the monomer in the photoinitiator initiation system in material or oligomer chemically react, rapid to cure, and layer upon layer obtains
Formation of parts.
In photocuring 3D printing forming technique, the selection of light source depends primarily upon suction of the photoinitiator to different frequency photon
Receive.The absorption coefficient of light of most photoinitiators in ultra-violet (UV) band is larger, is easy to make material solidification in ultraviolet region, thus, it is ultraviolet
Laser is current most common light source.However, the shortcomings of Ultra-Violet Laser light source is there are safety issue, and cost of manufacture is high, this
Limit its application.And visible laser have penetration capacity is strong, energy is big, efficiency of initiation is high, stability is good, more importantly, peace
The advantages that performance is high entirely a, it is considered to be important trend of future development.Therefore, develop new sensitive to wavelength visible
Photoinitiator system and photo-curing material become technical problem urgently to be resolved hurrily.
The content of the invention
The object of the present invention is to provide a kind of new photoinitiator for 3D printing to wavelength visible sensitivity
Composition.The initiator composition can be such that material cures under visible light, need to adopt to solve photoinitiator in the prior art
The existing safety problem with ultraviolet excitation.The initiator composition can be such that material cures in a short time, suitable for 3D
The requirement of printing device.
In order to realize the object of the invention, provided by the present invention for 3D printing technique by visible light-initiated photoinitiator
Composition, by key light initiator and helping photoinitiator to form, wherein key light initiator and to help the weight ratio of photoinitiator be 1:
0.1-10, preferably 1:0.2-2.
Wherein, the key light initiator is iodine salt compounds, sulphur salt compounds or their any mixture.
The iodine salt compounds include diaryl group iodized salt, aryl alkyl salt compounded of iodine, alkyl salt compounded of iodine, are preferably Diaryl iodonium
Salt, more preferably diphenyl iodnium hexafluorophosphate etc..The sulphur salt compounds include triaryl sulfonium salts, diaryl
Sulfosalt, alkyl sulfosalt, are preferably triaryl sulfonium salts, more preferably triphenyl sulfosalt hexafluorophosphate etc..
It is described to help shown in the structural formula such as formula (I) of photoinitiator：
In formula (I), R is selected from H, Cl, Br, I, NO2In one or more, M is selected from H, Na, K, Li, NH4In one kind or
It is a variety of.
It is described that to help photoinitiator be preferably eosin, eosin disodium salt.
The present invention also provides application of the photoinitiator composite in 3D printing optical soliton interaction technology.
The present invention also provides the photo-curing material prepared by the photoinitiator composite, wherein, the photoinitiator group
Compound accounts for the 0.1-10wt% of photo-curing material gross weight, preferably 1-5wt%.
The photo-curing material of the present invention can be made of each component of following parts by weight：
Wherein, the prepolymer of the unsaturated group containing alkenes is epoxy acrylate, urethane acrylate, polyester third
Olefin(e) acid ester, polyether acrylate or their any mixture.The epoxy acrylate is epoxy resin and unsaturated carboxylic acid
The addition compound product of reaction, is preferably epoxy acrylate, the propylene oxide of novolac epoxy resin of bisphenol A type epoxy resin
Acid esters.The urethane acrylate be by the acrylate of hydroxyl and the reaction product of polyalcohol and polyisocyanates into
Reactant made from row reaction, wherein the acrylate of the hydroxyl includes acrylic acid hydroxy alkyl ester, the polyalcohol includes
Ethylene glycol, propane diols etc., the polyisocyanates is including toluene di-isocyanate(TDI) etc..The polyester acrylate is polyester polyols
The condensation product of alcohol and acrylic acid, wherein the polyester polyol is the reaction product of polyalcohol and binary acid, the polyalcohol
Including ethylene glycol, propane diols etc..The binary acid is including adipic acid etc..The polyether acrylate includes two propylene of polyethylene glycol
Acid esters etc..
The monomer of the unsaturated group containing alkenes is acrylic ester compound, vinyl ethers compound, epoxies
Compound or their any mixture.The monomer of the unsaturated group containing alkenes includes butyl acrylate, acrylic acid -2- hydroxyls
Ethyl ester, 1,6 hexanediol diacrylate, tri (propylene glycol) diacrylate, Tetraethylene glycol diacrylate, three hydroxyls
Propane tri etc..
Other auxiliary agents include filler, pigment, antioxidant, defoamer, wetting agent, polymerization inhibitor or their any mixture.
Wherein, the filler includes talcum powder, silica etc..The pigment includes inorganic pigment, such as titanium dioxide, carbon black, phthalocyanine blue
Deng, or organic pigment, it is such as bright red.The antioxidant included for four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] seasons
Doutrate (antioxidant 1010), β-positive octadecanol ester (antioxidant 1076) of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid,
Three (2,4- di-tert-butyl-phenyls) phosphite esters (irgasfos 168), double (2,4- DI-tert-butylphenol compounds) pentaerythrite diphosphorous acids
Ester (antioxidant 626) etc..The defoamer includes organic silicon modified by polyether, higher alcohols, dimethyl silicone polymer etc..The inhibition
Agent includes quinhydrones, Hydroquinone monomethylether, hydroquinone, p-hydroxyanisole etc..
The solvent used in the photo-curing material of the present invention is selected from dimethyl sulfoxide (DMSO), methanol, ethanol, tetrahydrofuran, toluene
Deng organic solvent.
The present invention further provides application of the photo-curing material in 3D printing optical soliton interaction technology.The light is consolidated
Change material to be ejected by 3D printer nozzle bore, after visible light source irradiates or scans, obtain formation of parts.
Wherein described visible light source includes the laser or monochromatic visible light light source that emission wavelength is 480nm-600nm.Institute
State laser or monochromatic visible light light source include solid light source (such as laser diode), thermoluminescence light source (such as incandescent lamp,
Halogen lamp etc.), glow discharge spot lamp (such as fluorescent lamp, metal halide).
The emission wavelength of the light source is preferably 500nm-550nm, more preferably 520nm-540nm.Light source is most preferably
The green solid lighting source of 530nm.
The present invention has the following advantages：
(1) it is provided by the invention that photocuring 3D printing shaping skill is suitable for by visible light-initiated photoinitiator composite
Photo-curing material used in art.
(2) ultraviolet light-initiated photoinitiator is commonly used with 3D printing forming technique and combines difference, photoinitiator combination can
The light sources such as the laser of visible ray green light band with 500nm-550nm trigger, safe.
(3) photoinitiator composite only by specific structure key light initiator and help photoinitiator to form.Compare and its
Similar to system, the combining structure is different and relatively simple for it, without adding the third component such as electron donor, without pretreatment into
The structure such as salt composite in eosin salt compounded of iodine.
Embodiment
Following embodiments are used to illustrate the present invention, but are not limited to the scope of the present invention.Unless otherwise specified, embodiment
In the conventional means that are well known to those skilled in the art of used technological means, raw materials used is commercial goods.
Embodiment by visible light-initiated photoinitiator composite and contains the photoinitiator group for 3D printing technique
The photo-curing material of compound
Following embodiments offer by visible light-initiated photoinitiator composite and contains this for 3D printing technique
The photo-curing material of photoinitiator composite, specific formula are shown in Table 1.
Table 1
The various composition of various embodiments above is mixed in proportion, up to photo-curing material.Obtained photo-curing material by
3D printer nozzle bore ejects, and after light source is scanned on photo-curing material surface, the photoinitiator in material triggers system
In monomer or prepolymer chemically react, rapid to cure, layer upon layer obtains formation of parts.
The visible light source includes the laser or monochromatic visible light light source that emission wavelength is 480nm-600nm.It is described to swash
Light or monochromatic visible light light source include solid light source (such as laser diode), thermoluminescence light source (such as incandescent lamp, halogen
Lamp etc.), glow discharge spot lamp (such as fluorescent lamp, metal halide).
The emission wavelength of the light source is preferably 500nm-550nm, more preferably 520nm-540nm.Light source is most preferably
The green solid lighting source of 530nm.
With green solid lighting source (the diode pumping Nd of 530nm:YAG green (light) lasers) to various embodiments above
After photo-curing material surface is scanned, obtained part performance parameter is shown in Table 2.
Table 2
Embodiment described above is only to absolutely prove the preferred embodiment of the invention enumerated, protection scope of the present invention
Not limited to this.The equivalent substitute or conversion that those skilled in the art are made on the basis of the present invention, the present invention's
Within protection domain.
Claims (10)
1. for 3D printing technique by visible light-initiated photoinitiator composite, it is characterised in that by key light initiator and
Help photoinitiator to form, wherein key light initiator and help photoinitiator weight ratio be 1:0.1-10, preferably 1:0.2-2；
The key light initiator is iodine salt compounds, sulphur salt compounds or their any mixture；
It is described to help shown in the structural formula such as formula (I) of photoinitiator：
In formula (I), R is selected from H, Cl, Br, I, NO2In one or more, M is selected from H, Na, K, Li, NH4In one or more.
2. photoinitiator composite according to claim 1, it is characterised in that the iodine salt compounds include two virtues
Base salt compounded of iodine, aryl alkyl salt compounded of iodine, alkyl salt compounded of iodine, are preferably diaryl group iodized salt, more preferably diphenyl iodnium six
Fluorophosphate；The sulphur salt compounds include triaryl sulfonium salts, diaryl sulfosalt, alkyl sulfosalt, are preferably three
Arylsulfonium salts, more preferably triphenyl sulfosalt hexafluorophosphate.
3. photoinitiator composite according to claim 1 or 2, it is characterised in that described to help photoinitiator as eosin, daybreak
Red disodium salt.
4. application of any one of the claim 1-3 photoinitiator composites in 3D printing optical soliton interaction technology.
5. the photo-curing material prepared by any one of the claim 1-3 photoinitiator composites, it is characterised in that the light
Initiator composition accounts for the 0.1-10wt% of photo-curing material gross weight, preferably 1-5wt%.
6. photo-curing material according to claim 5, it is characterised in that be made of each component of following parts by weight：
Wherein, the prepolymer of the unsaturated group containing alkenes is epoxy acrylate, urethane acrylate, polyester acrylic
Ester, polyether acrylate or their any mixture；
The monomer of the unsaturated group containing alkenes is acrylic ester compound, vinyl ethers compound, epoxies chemical combination
Thing or their any mixture；
Other auxiliary agents include filler, pigment, antioxidant, defoamer, polymerization inhibitor or their any mixture；
The solvent is selected from dimethyl sulfoxide (DMSO), methanol, ethanol, tetrahydrofuran or toluene.
7. photo-curing material according to claim 6, it is characterised in that the epoxy acrylate is epoxy resin and not
The addition compound product of saturated carboxylic acid reaction, is preferably epoxy acrylate, the novolac epoxy resin of bisphenol A type epoxy resin
Epoxy acrylate；
The urethane acrylate be by the acrylate of hydroxyl and the reaction product of polyalcohol and polyisocyanates into
Reactant made from row reaction, wherein the acrylate of the hydroxyl includes acrylic acid hydroxy alkyl ester, the polyalcohol includes
Ethylene glycol, propane diols, the polyisocyanates include toluene di-isocyanate(TDI)；
The polyester acrylate is the condensation product of polyester polyol and acrylic acid, wherein the polyester polyol is polyalcohol
With the reaction product of binary acid, the polyalcohol includes ethylene glycol, propane diols, and the binary acid includes adipic acid；
The polyether acrylate includes polyethyleneglycol diacrylate.
8. photo-curing material according to claim 6, it is characterised in that the monomer of the unsaturated group containing alkenes includes
Butyl acrylate, acrylic acid -2- hydroxyl ethyl esters, 1,6 hexanediol diacrylate, tri (propylene glycol) diacrylate, three contractings four
Glycol diacrylate, trimethylolpropane trimethacrylate.
9. photo-curing material according to claim 6, it is characterised in that the filler includes talcum powder, silica；
The pigment includes titanium dioxide, carbon black, phthalocyanine blue, bright red；
The antioxidant includes four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, β-(bis- tertiary fourths of 3,5-
Base -4- hydroxy phenyls) the positive octadecanol ester of propionic acid, three (2,4- di-tert-butyl-phenyls) phosphite esters, double (2,4- di-tert-butyls
Phenol) pentaerythritol diphosphites；
The defoamer includes organic silicon modified by polyether, higher alcohols, dimethyl silicone polymer；
The polymerization inhibitor includes quinhydrones, Hydroquinone monomethylether, hydroquinone, p-hydroxyanisole.
10. application of any one of the claim 5-9 photo-curing materials in 3D printing optical soliton interaction technology, its feature exist
In the photo-curing material is ejected by 3D printer nozzle bore, after visible light source irradiates or scans, obtains shaping zero
Part；
Wherein described visible light source includes the laser or monochromatic visible light light source that emission wavelength is 480nm-600nm；It is described to swash
Light or monochromatic visible light light source include solid light source, thermoluminescence light source, glow discharge spot lamp；
The emission wavelength of light source is preferably 500nm-550nm, more preferably 520nm-540nm；
Light source is most preferably the green solid lighting source of 530nm.
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