CN106608952A - Flexible light-cured resin material for 3D printing and preparation method and application thereof - Google Patents
Flexible light-cured resin material for 3D printing and preparation method and application thereof Download PDFInfo
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- CN106608952A CN106608952A CN201611075110.XA CN201611075110A CN106608952A CN 106608952 A CN106608952 A CN 106608952A CN 201611075110 A CN201611075110 A CN 201611075110A CN 106608952 A CN106608952 A CN 106608952A
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- Prior art keywords
- printing
- resin material
- photocurable resin
- parts
- flexible
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- 238000010146 3D printing Methods 0.000 title claims abstract description 48
- 239000011347 resin Substances 0.000 title claims abstract description 47
- 229920005989 resin Polymers 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 125000004386 diacrylate group Chemical group 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 150000002148 esters Chemical class 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- SYENVBKSVVOOPS-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl prop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C=C SYENVBKSVVOOPS-UHFFFAOYSA-N 0.000 claims description 3
- ZMDDERVSCYEKPQ-UHFFFAOYSA-N Ethyl (mesitylcarbonyl)phenylphosphinate Chemical group C=1C=CC=CC=1P(=O)(OCC)C(=O)C1=C(C)C=C(C)C=C1C ZMDDERVSCYEKPQ-UHFFFAOYSA-N 0.000 claims description 3
- HOCOIDRZLNGZMV-UHFFFAOYSA-N ethoxy(oxido)phosphanium Chemical compound CCO[PH2]=O HOCOIDRZLNGZMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- 241001502050 Acis Species 0.000 claims description 2
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 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 1
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 claims 1
- XRKRLGIKBFGWKI-UHFFFAOYSA-N butane;prop-2-enoic acid Chemical compound CCCC.OC(=O)C=C XRKRLGIKBFGWKI-UHFFFAOYSA-N 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 239000003999 initiator Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000012188 paraffin wax Substances 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 230000008676 import Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000007711 solidification Methods 0.000 description 9
- 230000008023 solidification Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- QFGLGXAWPPBRHQ-UHFFFAOYSA-N 2,2-dimethylbutane;prop-2-enoic acid Chemical compound OC(=O)C=C.CCC(C)(C)C QFGLGXAWPPBRHQ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005491 wire drawing Methods 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XHIKSLHIZYVEQI-UHFFFAOYSA-N CC1=C(C(=O)[PH2]=O)C(=CC(=C1)C)C Chemical class CC1=C(C(=O)[PH2]=O)C(=CC(=C1)C)C XHIKSLHIZYVEQI-UHFFFAOYSA-N 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- -1 methoxyl group Chemical group 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 2
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 description 1
- IJLKRBGCMSMLCY-UHFFFAOYSA-N C(C)OP(=O)(C1=CC=CC=C1)S(=O)(=O)N Chemical compound C(C)OP(=O)(C1=CC=CC=C1)S(=O)(=O)N IJLKRBGCMSMLCY-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- BGNAJQRJXQBCDF-UHFFFAOYSA-N [ethoxy-(2,3,4-trimethylphenyl)phosphoryl]-phenylmethanone Chemical compound C=1C=C(C)C(C)=C(C)C=1P(=O)(OCC)C(=O)C1=CC=CC=C1 BGNAJQRJXQBCDF-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 238000000110 selective laser sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic 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
- 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
-
- 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
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
Abstract
The invention discloses a flexible light-cured resin material for 3D printing and a preparation method and application thereof. The flexible light-cured resin material is prepared from the following raw materials in parts by weight: 10-99 parts of polymerization monomers, 1-4 parts of photoinitiator, 8-36 parts of reaction auxiliaries, 0.1-1 part of lubricant and 0.1-0.5 part of polymerization inhibitor. The preparation method disclosed by the invention is simple and is easy in operation and high in yield. The current situation that consumables of DLP and SLA equipment for 3D printing basically depend on import at present is solved, and the problem that materials for 3D printing are high in manufacturing cost is further solved, so that light-cured resin for 3D printing in our country does not depend on import any more, and the scientific significance and application value are great.
Description
Technical field
The invention belongs to photocurable resin material field, more particularly to a kind of flexible photocuring tree for being applied to 3D printer
Fat material and preparation method thereof.
Background technology
Light-cured resin superior performance, the material is similar to traditional engineering plastics (including ABS and PBT etc.).It can quilt
Preferably apply in automobile, medical apparatus and instruments, the exemplar of daily electronic product makes, be also apply to discharge analysis, room temperature sulfur
The aspects such as SiClx rubber cast, the conceptual model that can be deposited, airduct test, quick cast model.3D light-cured resins in contrast to
Conventional thermoplastic's 3D printing material, with time-write interval short (be its 1/20), product surface is smooth without wire drawing, and quality is full, produces
Product surface is fine and smooth, many advantages, such as can be used for biomaterial.
Photocuring system has the advantages that pollution-free, avirulence, non-stimulated and production safety, is at present more active grinding
Study carefully and development field, base becomes one of main development direction of UV-curing technology.3D printing is alternatively referred to as increasing material manufacturing skill
Art, the appearance of 3D printing makes manufacture complex parts become easily and quickly.At present, the 3D printing technique of comparative maturity mainly has
" fuse deposition rapid forming ", " quires layer rapid shaping ", " selective laser sintering rapid forming " and " stereolithography is rapid-result soon
Type ".Earliest, it is stereolithography rapid shaping to be most widely used for industrial 3D printing technique, and it is purple using computer controls
Outer laser presses the shape point by point scanning of two-dimensional section on photosensitive resin liquid level, makes resin solidification, and the resin after solidification is just formed
One X-Y scheme, so successively scans, solidification, complete 3D solid is finally obtained and (is commonly called as:Part).Part quality
Quality depend primarily on the quality of photosensitive resin performance, it is 3D printing to develop the good photosensitive resin of performance, and three-dimensional printing is quick
Forming technique study hotspot.Three-dimensional quick shaping 3D printing technique with photosensitive resin as raw material, with low cost, high precision,
The advantages of molding is fast, is widely used in every field.
The content of the invention
Present invention aim at offer is a kind of to be applied to flexible light-cured resin of 3D printing and preparation method thereof, solve
3D printing at present relies on the present situation of import with the consumptive material of DLP, SLA equipment substantially, further solves 3D printing material construction high
Problem so that China's 3D printing light-cured resin is no longer dependent on import, with great scientific meaning and apply valency
Value；Easy to operate and preparation method is simple, yield is high.
The technical solution used in the present invention is：
A kind of 3D printing is made by weight ratio with flexible photocurable resin material, including following raw material：Polymerized monomer
10-99 parts, light trigger 1-4 parts, reaction promoter 8-36 parts, lubricant 0.1-1 parts and polymerization inhibitor 0.1-0.5 parts.
A kind of described 3D printing with flexible photocurable resin material, described polymerized monomer be epoxy acrylic resin,
The combination of one or two or more kinds in aliphatic urethane acrylate, Polyethylene Glycol (400) diacrylate.
A kind of described 3D printing is 2,4,6- trimethylbenzene first with flexible photocurable resin material, described light trigger
Double (the 2,4,6- trimethylbenzoyls of aminosulfonylphenyl phosphinic acid ethyl ester, (2,4,6- trimethylbenzoyls) diphenyl phosphine oxide, phenyl
Base) combination of one or two or more kinds in phosphine oxide.
A kind of described 3D printing flexibility photocurable resin material, described light trigger is 4, the 6- trimethylbenzenes by 2
Fonnylphenyl phosphinic acid ethyl ester and double (2,4,6- trimethylbenzoyls) phosphine oxides by ratio of weight and the number of copies 1 of phenyl:1 ratio group
Into.
A kind of described 3D printing is 1- amyl group -3- methyl miaows with flexible photocurable resin material, described reaction promoter
Azoles perrhenate, 1- amyl group -3- Methylimidazole. acetate, divinylbenzene, trihydroxy first propane triacrylate, two contractings 3 third
The combination of one or two or more kinds in omega-diol diacrylate and double trimethylolpropane acrylate.
A kind of described 3D printing flexibility photocurable resin material, described reaction promoter is by 1- amyl group -3- methyl miaows
Azoles perrhenate, 1- amyl group -3- Methylimidazole. acetate, divinylbenzene and double trimethylolpropane acrylate are by weight
Number compares 0.1-0.2：0.1-0.2：5-15：The ratio composition of 3-20.
A kind of described 3D printing is zinc stearate, esters of silicon acis, stone with flexible photocurable resin material, described lubricant
One or two or more kinds combination in wax or stearic acid.
A kind of described 3D printing flexibility photocurable resin material, described polymerization inhibitor is for phenol and/or to methoxyl group
Phenol.
The 3D printing preparation method of flexible photocurable resin material, comprises the steps：
1) first nitrogen is passed through by polymerized monomer addition reactor, is stirred, controlling reaction temperature 50-70 DEG C；
2) in reactor reaction promoter and lubricant are slowly added to again, are warming up to 80-100 DEG C, stirred；
3) it is slowly added to light trigger in reactor and then again, polymerization inhibitor, keeping temperature, stirring reaction is after 0.5 hour,
Reaction terminates, cooling, obtains target product.
Application of the described 3D printing with flexible photocurable resin material in 3D printer.
The invention has the advantages that：The 3D printing of the present invention flexible photocurable resin material, preparation technology tool
There is method simple, easy to operate, yield is high, the advantages of environmental pollution is little.The present invention solves the synthesis of 3D printing light-cured resin
Difficulty, the problem of low yield, and further solve the problems, such as that 3D printing resin cost is high, so that China 3D printing tree
Fat is no longer dependent on import, with great scientific meaning and using value.
Specific embodiment
A kind of 3D printing is made by weight ratio with flexible photocurable resin material, including following raw material：
A kind of above-mentioned 3D printing preparation method of flexible photocurable resin material, comprises the steps：
1) in the reactor equipped with agitator, condenser, thermometer and charging spout, epoxy acrylic resin and fat are added
Fat adoption urethane acrylate, is passed through nitrogen, stirs, Deca Polyethylene Glycol (400) diacrylate, controlling reaction temperature
50-70 DEG C, continue to stir after completion of dropping.
2) it is slowly added to divinylbenzene, double trimethyl propane acrylate, 1- amyl group -3- Methylimidazole. perrhenates,
1- amyl group -3- Methylimidazole. acetate, zinc stearate is warming up to 80-100 DEG C, stirs.
3) 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl esters, double (2,4, the 6- trimethylbenzoyls of phenyl are slowly added to
Base) phosphine oxide, p methoxy phenol, keeping temperature, after 0.5 hour, reaction terminates stirring reaction, cooling, obtains target product.
A kind of 3D printing of embodiment 1 flexibility photocurable resin material
(1) it is made up by weight ratio of following raw material：25 parts of epoxy acrylic resin, aliphatic polyurethane acrylic acid
15 parts of ester, 30 parts of Polyethylene Glycol (400) diacrylate, 5 parts of divinylbenzene, 5 parts of double trimethyl propane acrylate, 1- penta
0.1 part of base -3- Methylimidazole .s perrhenate, 0.1 part of 1- amyl group -3- Methylimidazole .s acetate, 0.5 part of zinc stearate, 2,4,6-
1 part of trimethylbenzoyl phenyl phosphinic acid ethyl ester, double 1 part of (2,4,6- trimethylbenzoyl) phosphine oxides of phenyl, to methoxyl group
0.2 part of phenol.
(2) preparation method
1) in the reactor equipped with agitator, condenser, thermometer and charging spout, epoxy acrylic resin and fat are added
Fat adoption urethane acrylate, is passed through nitrogen, stirs, Deca Polyethylene Glycol (400) diacrylate, controlling reaction temperature
50-70 DEG C, continue to stir after completion of dropping.
2) it is slowly added to divinylbenzene, double trimethyl propane acrylate, 1- amyl group -3- Methylimidazole. perrhenates,
1- amyl group -3- Methylimidazole. acetate, zinc stearate is warming up to 80-100 DEG C, stirs.
3) 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl esters, double (2,4, the 6- trimethylbenzoyls of phenyl are slowly added to
Base) phosphine oxide, p methoxy phenol, keeping temperature, stirring.After reaction 0.5 hour, reaction terminates, cooling, obtains target product.
(3) testing result
Target product prepared by the present embodiment be clear pale yellow color thick liquid, density:1.08-1.13g/cm3, solidification
Front boiling point:>100 DEG C, flash-point before solidification:>100 DEG C, viscosity before solidification:650-800 CPS(25℃).
(4) apply
By in liquid bath of the 3D printing prepared by the present embodiment with flexible light-cured resin injection printer, treat its liquid level certainly
So after levelling, start printing.The product that this resin is printed, quality is full, and surface is fine and smooth, without wire drawing phenomenon, tool
There is good elasticity.
A kind of 3D printing of embodiment 2 flexibility photocurable resin material
(1) it is made up by weight ratio of following raw material：35 parts of epoxy acrylic resin, aliphatic polyurethane acrylic acid
30 parts of ester, 40 parts of Polyethylene Glycol (400) diacrylate, 15 parts of divinylbenzene, 10 parts of double trimethyl propane acrylate, 1-
0.2 part of amyl group -3- Methylimidazole .s perrhenate, 0.2 part of 1- amyl group -3- Methylimidazole .s acetate, 0.5 part of zinc stearate, 2,4,
2 parts of 6- trimethylbenzoyl phenyls phosphinic acid ethyl ester, double 2 parts of (2,4,6- trimethylbenzoyl) phosphine oxides of phenyl, to methoxy
0.2 part of base phenol.
(2) preparation method
With embodiment 1.
(3) testing result
Target product prepared by the present embodiment be clear pale yellow color thick liquid, density:1.08-1.13g/cm3, solidification
Front boiling point:>100 DEG C, flash-point before solidification:>100 DEG C, viscosity before solidification:650-800 CPS(25℃).
(4) apply
By in liquid bath of the 3D printing prepared by the present embodiment with flexible light-cured resin injection printer, treat its liquid level certainly
So after levelling, start printing.The product that this resin is printed, quality is full, and surface is fine and smooth, without wire drawing phenomenon, tool
There is good elasticity.
Claims (10)
1. a kind of 3D printing is with flexible photocurable resin material, it is characterised in that make by weight ratio including following raw material：
Polymerized monomer 10-99 part, light trigger 1-4 parts, reaction promoter 8-36 parts, lubricant 0.1-1 parts and polymerization inhibitor 0.1-0.5 parts.
2. a kind of 3D printing as claimed in claim 1 is with flexible photocurable resin material, it is characterised in that described polymerization list
Body is the one kind in epoxy acrylic resin, aliphatic urethane acrylate, Polyethylene Glycol (400) diacrylate or two kinds
Combination above.
3. a kind of 3D printing as claimed in claim 1 is with flexible photocurable resin material, it is characterised in that described is light-initiated
Agent is 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl esters, (2,4,6- trimethylbenzoyls) diphenyl phosphine oxide, phenyl
The combination of one or two or more kinds in double (2,4,6- trimethylbenzoyls) phosphine oxides.
4. a kind of 3D printing as described in claim 1 or 3 is with flexible photocurable resin material, it is characterised in that described light
Initiator is by 2,4,6- trimethylbenzoyl phenyls phosphinic acid ethyl ester and phenyl double (2,4,6- trimethylbenzoyls) oxidation
Phosphine by ratio of weight and the number of copies 1:1 ratio composition.
5. a kind of 3D printing as claimed in claim 1 is with flexible photocurable resin material, it is characterised in that described reaction is helped
Agent is 1- amyl group -3- Methylimidazole. perrhenates, 1- amyl group -3- Methylimidazole. acetate, divinylbenzene, trihydroxy first propane
One or two or more kinds in triacrylate, tri (propylene glycol) diacrylate and double trimethylolpropane acrylate
Combination.
6. a kind of 3D printing as described in claim 1 or 5 is with flexible photocurable resin material, it is characterised in that described is anti-
Auxiliary agent is answered by 1- amyl group -3- Methylimidazole. perrhenates, 1- amyl group -3- Methylimidazole. acetate, divinylbenzene and double three hydroxyls
Methylpropane acrylate 0.1-0.2 by ratio of weight and the number of copies：0.1-0.2：5-15：The ratio composition of 3-20.
7. a kind of 3D printing as claimed in claim 1 is with flexible photocurable resin material, it is characterised in that described lubricant
Combine for one or two or more kinds in zinc stearate, esters of silicon acis, paraffin or stearic acid.
8. a kind of 3D printing as claimed in claim 1 is with flexible photocurable resin material, it is characterised in that described polymerization inhibitor
For phenol and/or p methoxy phenol.
9. the 3D printing preparation method of flexible photocurable resin material as described in claim 1-8, it is characterised in that include as
Lower step：
1) first nitrogen is passed through by polymerized monomer addition reactor, is stirred, controlling reaction temperature 50-70 DEG C；
2) in reactor reaction promoter and lubricant are slowly added to again, are warming up to 80-100 DEG C, stirred；
3) it is slowly added to light trigger in reactor and then again, polymerization inhibitor, keeping temperature, stirring reaction is after 0.5 hour, reaction
Terminate, cooling obtains target product.
10. application of the 3D printing as described in claim 1-8 with flexible photocurable resin material in 3D printer.
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| CN107312135A (en) * | 2017-08-09 | 2017-11-03 | 长沙远达华信息科技有限公司 | A kind of 3D printing flexible photocurable resin material and its preparation method and application |
| CN111285695A (en) * | 2020-02-24 | 2020-06-16 | 东莞职业技术学院 | Rapid prototyping-based 3D printing zirconia ceramic photocuring resin |
| CN114341280A (en) * | 2019-07-12 | 2022-04-12 | 3D系统公司 | Building material for 3D printing |
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Application publication date: 20170503 |