CN112608429A - Pretreatment dual-curing 3D printing resin and pretreatment method thereof - Google Patents
Pretreatment dual-curing 3D printing resin and pretreatment method thereof Download PDFInfo
- Publication number
- CN112608429A CN112608429A CN202011397781.4A CN202011397781A CN112608429A CN 112608429 A CN112608429 A CN 112608429A CN 202011397781 A CN202011397781 A CN 202011397781A CN 112608429 A CN112608429 A CN 112608429A
- Authority
- CN
- China
- Prior art keywords
- printing resin
- curing
- resin according
- printing
- pretreatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011347 resin Substances 0.000 title claims abstract description 36
- 229920005989 resin Polymers 0.000 title claims abstract description 36
- 238000010146 3D printing Methods 0.000 title claims abstract description 32
- 238000002203 pretreatment Methods 0.000 title claims abstract description 15
- 125000002091 cationic group Chemical group 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 238000007639 printing Methods 0.000 claims abstract description 8
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 150000003254 radicals Chemical class 0.000 claims abstract description 6
- -1 polysiloxane Polymers 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 230000005684 electric field Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 claims description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 3
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 3
- 239000012954 diazonium Substances 0.000 claims description 3
- 230000002045 lasting effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 claims description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 3
- 230000001678 irradiating effect Effects 0.000 claims 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 claims 1
- 238000001723 curing Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012656 cationic ring opening polymerization Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003568 thioethers Chemical class 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
- 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
- C08F283/01—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
- C08F283/06—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
-
- 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
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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 invention discloses a pretreatment dual-curing 3D printing resin and a pretreatment method thereof, wherein the pretreatment dual-curing 3D printing resin comprises the following raw materials in percentage by weight: 19-78% of oligomer, 1-9% of free radical initiator, 0.5-5% of cationic initiator, 0.5-5% of hybrid curing photoinitiator, 0.2-4% of auxiliary agent, 10-35% of reactive diluent, 13-62% of cationic monomer and 5-20% of hybrid monomer; the sum of the weight percentages of the components is 100 percent. The invention has the advantages of obtaining the printing effect which is comparable to that of a high-energy SLA sinking type 3D printer, low shrinkage rate, good curing performance, excellent mechanical property and convenient color changing, and solves the problems of huge material groove of the sinking type printer, large amount of required resin, high requirement on humidity control and the like.
Description
Technical Field
The invention relates to the technical field of 3D printing, in particular to a pretreatment dual-curing 3D printing resin and a pretreatment method thereof.
Background
With the popularization of 3D printing technology, DLP/SLA 3D printing technology is applied more and more, and more requirements are put forward on the physical properties of 3D printed products, and the photocuring 3D printing technology is a novel material processing and forming method which is based on a three-dimensional model and is a method for directly printing a solid model by adding materials layer by layer. The technology can print parts with diversified shapes and appearances and individuation without manufacturing a die, thereby greatly simplifying the production process of the product.
China CN201310498194.8 discloses various photo-curing 3D printing hybrid system photosensitive resins, which comprise the following raw material components in parts by mass: the oligomer A, the oligomer B and the acrylic ester are mixed according to the mass percentage of 50: 15: 35, the mixture accounts for 70 to 90 percent of the total mass of the active components; the active diluent accounts for 10 to 30 percent of the total mass of the active components; the oligomer A, the oligomer B and the acrylic ester are mixed according to the mass percentage of 50: 15: 35 and the total mass of the active diluent is 100 percent; auxiliary agent: the cationic initiator accounts for 1-10% of the total mass of the active components, the free radical initiator accounts for 1-6% of the total mass of the active components, the accelerator accounts for 1-8% of the total mass of the active components, the leveling agent accounts for 0.05-1.0% of the total mass of the active components, and the defoaming agent accounts for 0.05-1.0% of the total mass of the active components; the invention can print out objects with high precision and arbitrary shapes, and then can not reach the energy and high energy (20000-2) The SLA sinking type 3D printer has the printing effect which is comparable to that of the prior printed products, the shrinkage rate is high, the curing performance is poor, the mechanical property is poor, the color changing is inconvenient, the amount of resin required during printing is large, and the requirement on humidity control is high.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a pretreatment dual-curing 3D printing resin and a pretreatment method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the pretreatment dual-curing 3D printing resin comprises the following raw materials in percentage by weight: 19-78% of oligomer, 1-9% of free radical initiator, 0.5-5% of cationic initiator, 0.5-5% of hybrid curing photoinitiator, 0.2-4% of auxiliary agent, 10-35% of reactive diluent, 13-62% of cationic monomer and 5-20% of hybrid monomer; the sum of the weight percentages of the components is 100 percent.
The oligomer is selected from one or more of epoxy acrylate, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy functionalized polysiloxane resin.
The free radical initiator is selected from one or more of photoinitiators 1173, 184, 907, TPO, 651, 819, 369, DETX, 784.
The cationic initiator is selected from one or more of aryl diazonium salt, diaryl iodonium salt, triaryl sulfonium salt and aryl ferrocenium salt.
The hybrid curing photoinitiator is selected from one or more of Omnica 550 and Omnica 650 in Jiu.
The active diluent is selected from one or more of isobornyl acrylate (IBOA), tetrahydrofuran acrylate (THFA), isodecyl acrylate (IDA), tridecyl acrylate (TDA), polyethylene glycol (400) diacrylate [ PEG (400) DA ], cyclotrimethylolpropane formal acrylate, 2-phenoxyethyl acrylate, cyclohexyl methacrylate, and (2) propoxylated neopentyl glycol diacrylate (NPG (PO)2 DA).
The cationic monomer is selected from one or more of GR-OX-1, GR-OX-2, GR-OX-3, GR-OX-4, GR-OX-6, GR-OX-8 and GR-OX-11 of Hubei Gurun science and technology Limited.
The hybrid monomer is selected from one or more of OXE-10 of Osaka organic chemistry, OXE-30 of Osaka organic chemistry, 6270 of Changxing chemical industry Co., Ltd, and 6278 of Changxing chemical industry Co., Ltd, and can simultaneously undergo radical polymerization and cationic ring-opening polymerization.
The auxiliary agent comprises a leveling agent and a defoaming agent, and the leveling agent is selected from one or more of polydimethylsiloxane, polymethylphenylsiloxane and organic silicon modified polysiloxane; the leveling agent is selected from: BYK-UV333 manufactured by BYK company, BYK-3510, BYK-066N or MOK-2120 manufactured by Merck company of Germany, and B-0520 manufactured by Federal chemical company of China.
The invention also provides a pretreatment method for pretreating the dual-curing 3D printing resin, which comprises the following steps:
step 1, pretreatment: under the condition that the temperature is less than or equal to 30 ℃, the raw materials in the proportion are stirred at low speed of 450-550r/min, and an external direct current weak electric field of 10-50A/m is applied2And lasting for 2-10min, and measuring the viscosity of the mixture materials by a rotary viscometer: 150-;
step 2, transferring the pretreated proportioning material to a DLP/LCD-3D printer, heating the printer module to 35-45 ℃, and then carrying out low-energy (1-20 mw/cm)2)365-2) Compared with the SLA sinking type 3D printer, the SLA sinking type 3D printer has the advantages of good printing effect, low shrinkage rate, good curing performance, excellent mechanical property and convenient color changing, and solves the problems of huge material groove, large amount of required resin, high requirement on humidity control and the like of the sinking type printer.
By adopting the technical scheme of the invention, the invention has the following beneficial effects: the invention can obtain high energy (20000-2) Compared with the SLA sinking type 3D printer, the SLA sinking type 3D printer has the advantages of good printing effect, low shrinkage rate, good curing performance, excellent mechanical property and convenient color changing, and solves the problems of huge material groove, large amount of required resin, high requirement on humidity control and the like of the sinking type printer.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
39g of epoxy acrylate,
Cationic monomer GR-OX-118 g,
OXE-10 15g、
NPG(PO)2DA 11.5g、
2.5g of aryl diazonium salt,
Omnicat550 1g、
1845 g of photoinitiator,
Omnicat 5505 g for a long time,
MOK-2120 2g、
BYK-066N 1g
The total amount is 100 g.
Under the condition that the temperature is less than or equal to 30 ℃, 100g of the pretreated dual-curing 3D printing resin (the raw materials in the proportion) is stirred at a low speed of 500r/min, and an external direct current weak electric field of 50A/m is applied2And lasting for 10min to obtain the pretreated dual-curing 3D printing resin, transferring the pretreated proportioning material to a DLP-3D printer, heating the printer module to 35 ℃, and then performing low-energy (15 mw/cm)2) The printed film was irradiated with 405nm ultraviolet light, and then the properties thereof were tested by the following evaluation methods.
Example 2:
41g of polyester acrylate,
Cationic monomer GR-OX-416 g,
6270 14g、
Tridecyl acrylate 11.5g,
Diaryl iodonium salt 2.5g,
Omnicat550 1g、
5g of photoinitiator TPO,
Omnicat 5505 g for a long time,
BYK-333 2.5g、
BYK-3510 1.5g、
Total of 100g
Stirring 100g of the pretreated dual-curing 3D printing resin at a low speed of 500r/min at a temperature of less than or equal to 30 ℃, and applying an external direct-current weak electric field of 30A/m2Continuing for 10min, transferring the pretreated proportioning material to a DLP-3D printer, heating the printer module to 40 ℃, and then performing low-energy (18 mw/cm)2) The printed film was irradiated with 405nm ultraviolet light, and then the properties thereof were tested by the following evaluation methods.
Example 3:
42g of epoxy acrylate,
Cationic monomer GR-OX-816 g,
6278 15g、
THFA 13.5g、
Triaryl sulfide salt 2.5g,
Omnicat550 1g，
2g of photoinitiator TPO,
Omnicat650 5g、
MOK-2120 2g、
BYK-066N 1g、
Total of 100g
Stirring 100g of the pretreated dual-curing 3D printing resin at a low speed of 500r/min at a temperature of less than or equal to 30 ℃, and applying an external direct-current weak electric field of 45A/m2Continuing for 10min, transferring the pretreated proportioning material to a DLP-3D printer, heating the printer module to 42 ℃, and then carrying out low-energy (18 mw/cm)2) The ink was printed under irradiation of 385nm ultraviolet light and then tested for its properties according to the following evaluation methods.
Comparative example 1:
ordinary polyester epoxy acrylic resin photocuring 3D printing resin sample.
After passing through a DLP-3D printer, the temperature of a printer module is raised to 38 ℃, and then the temperature is reduced by low energy (20 mw/cm)2) The printed film was irradiated with 405nm ultraviolet light, and then the properties thereof were tested by the following evaluation methods.
Comparative example 2:
common polyether urethane acrylate photocuring 3D printing resin,
after passing through a DLP-3D printer, the temperature of a printer module is raised to 35 ℃, and then the temperature is reduced by low energy (20 mw/cm)2) The ink was printed under irradiation of 385nm ultraviolet light and then tested for its properties according to the following evaluation methods.
Comparative example 3:
commercially available cation curing SLA sinking type 3D printing resin produced by I department is printed by an SLA sinking type 3D printer.
The results of comparing the properties of the examples with those of general photocurable resins are shown in the following table 1:
TABLE 1
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Viscosity (cps/25 ℃ C.) | 255 | 265 | 260 | 280 | 270 | 260 |
| Photocuring Activity | Superior food | Superior food | Superior food | Good wine | Good wine | Superior food |
| Curing shrinkage (%) | 2.2 | 2.0 | 2.1 | 4.2 | 4.0 | 2.1 |
| Notched impact strength (KJ/m2) | 29.9 | 29.6 | 28.8 | 19.36 | 8.58 | 28.8 |
| Tensile Strength (MPa) | 42.2 | 45.2 | 41.5 | 25.6 | 24.9 | 41.5 |
| Elongation at Break (%) | 9 | 9.2 | 9.5 | 4 | 4.5 | 9.5 |
From the above-mentioned embodiments 1, 2, 3 and pairsThe proportion 1 and the proportion 2 show that the pretreated dual-curing 3D printing resin is transferred to a DLP/LCD-3D printer, the temperature of a printer module is raised to 35 to 45 ℃, and then the dual-curing 3D printing resin is subjected to low energy (1 to 20 mw/cm)2)365-2) Compared with the SLA sinking type 3D printer, the SLA sinking type 3D printer has the advantages of good printing effect (such as comparative example 3), low shrinkage rate, good curing performance, excellent mechanical property and convenient color changing, and solves the problems of huge material groove, large amount of required resin, high requirement on humidity control and the like of the sinking type printer.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. The pretreatment dual-curing 3D printing resin is characterized by comprising the following raw materials in percentage by weight: 19-78% of oligomer, 1-9% of free radical initiator, 0.5-5% of cationic initiator, 0.5-5% of hybrid curing photoinitiator, 0.2-4% of auxiliary agent, 10-35% of reactive diluent, 13-62% of cationic monomer and 5-20% of hybrid monomer; the sum of the weight percentages of the components is 100 percent.
2. The pre-treatment dual cure 3D printing resin according to claim 1, wherein the oligomer is selected from one or more of epoxy acrylates, urethane acrylates, polyester acrylates, polyether acrylates, epoxy functionalized polysiloxane resins.
3. The pre-treatment dual cure 3D printing resin according to claim 1, wherein the radical initiator is selected from one or more of the photoinitiators 1173, 184, 907, TPO, 651, 819, 369, DETX, 784.
4. The pre-treatment dual cure 3D printing resin according to claim 1, wherein the cationic initiator is selected from one or more of aryl diazonium salts, diaryl iodonium salts, triaryl sulfonium salts, aryl ferrocenium salts.
5. The pre-treatment dual cure 3D printing resin according to claim 1, wherein the hybrid curing photoinitiator is selected from one or more of jimmiat 550, omnica 650.
6. The pre-treatment dual cure 3D printing resin according to claim 1, wherein the reactive diluent is selected from one or more of isobornyl acrylate, tetrahydrofurfuryl acrylate, isodecyl acrylate, tridecyl acrylate, polyethylene glycol diacrylate, cyclotrimethylolpropane formal acrylate, 2-phenoxyethyl acrylate, cyclohexyl methacrylate, and (2) propoxylated neopentyl glycol diacrylate.
7. The pre-treatment dual cure 3D printing resin according to claim 1, wherein the cationic monomer is selected from one or more of GR-OX-1, GR-OX-2, GR-OX-3, GR-OX-4, GR-OX-6, GR-OX-8, GR-OX-11 from north Hu Gurun technologies, Inc.
8. The pre-treatment dual cure 3D printing resin according to claim 1, wherein the hybrid monomer is selected from one or more of OXE-10 of osaka organic chemistry, OXE-30 of osaka organic chemistry, 6270 of changxing chemical industry co.
9. The pre-treatment dual-curing 3D printing resin according to claim 1, wherein the auxiliary agent comprises a leveling agent and a defoaming agent, and the leveling agent is selected from one or more of polydimethylsiloxane, polymethylphenylsiloxane, and silicone modified polysiloxane.
10. A pre-treatment method for pre-treating a dual cure 3D printing resin according to claims 1-9, characterized by the steps of:
step 1, pretreatment: under the condition that the temperature is less than or equal to 30 ℃, the raw materials in the proportion are stirred at low speed of 450-550r/min, and an external direct current weak electric field of 10-50A/m is applied2And lasting for 2-10min, and measuring the viscosity of the mixture materials by a rotary viscometer: 150-350 MPa.s;
and 2, transferring the pretreated proportioning material to a DLP/LCD-3D printer, heating the printer module to 35-45 ℃, and irradiating by using low-energy 365-425nm ultraviolet light to obtain a printing effect comparable to that of a high-energy SLA sinking type 3D printer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011397781.4A CN112608429A (en) | 2020-12-03 | 2020-12-03 | Pretreatment dual-curing 3D printing resin and pretreatment method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011397781.4A CN112608429A (en) | 2020-12-03 | 2020-12-03 | Pretreatment dual-curing 3D printing resin and pretreatment method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112608429A true CN112608429A (en) | 2021-04-06 |
Family
ID=75228716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011397781.4A Pending CN112608429A (en) | 2020-12-03 | 2020-12-03 | Pretreatment dual-curing 3D printing resin and pretreatment method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112608429A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892549A (en) * | 2015-04-20 | 2015-09-09 | 南昌大学 | Synthesis method of allyl oxetane compound for ultraviolet light curing |
| CN106543649A (en) * | 2016-10-25 | 2017-03-29 | 北京化工大学 | One specific admixture type 3D printing light curing resin composition |
| US9902860B1 (en) * | 2016-08-30 | 2018-02-27 | Nano And Advanced Materials Institute Limited | Photopolymer composition for 3D printing |
| CN107987474A (en) * | 2017-11-21 | 2018-05-04 | 辽宁省轻工科学研究院 | A kind of light-cured resin and preparation method for rapid shaping |
| CN111690096A (en) * | 2020-05-20 | 2020-09-22 | 广西春景环保科技有限公司 | Preparation method of 3D printing photosensitive resin material |
| US20200308426A1 (en) * | 2017-12-19 | 2020-10-01 | Perstorp Ab | A hybrid photopolymer composition for additive manufacturing |
| CN111909491A (en) * | 2020-07-10 | 2020-11-10 | 广东工业大学 | Photosensitive composite resin for photocuring 3D printing and preparation method thereof |
-
2020
- 2020-12-03 CN CN202011397781.4A patent/CN112608429A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892549A (en) * | 2015-04-20 | 2015-09-09 | 南昌大学 | Synthesis method of allyl oxetane compound for ultraviolet light curing |
| US9902860B1 (en) * | 2016-08-30 | 2018-02-27 | Nano And Advanced Materials Institute Limited | Photopolymer composition for 3D printing |
| CN106543649A (en) * | 2016-10-25 | 2017-03-29 | 北京化工大学 | One specific admixture type 3D printing light curing resin composition |
| CN107987474A (en) * | 2017-11-21 | 2018-05-04 | 辽宁省轻工科学研究院 | A kind of light-cured resin and preparation method for rapid shaping |
| US20200308426A1 (en) * | 2017-12-19 | 2020-10-01 | Perstorp Ab | A hybrid photopolymer composition for additive manufacturing |
| CN111690096A (en) * | 2020-05-20 | 2020-09-22 | 广西春景环保科技有限公司 | Preparation method of 3D printing photosensitive resin material |
| CN111909491A (en) * | 2020-07-10 | 2020-11-10 | 广东工业大学 | Photosensitive composite resin for photocuring 3D printing and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 付文等: "快速光固化用阳离子光引发剂研究进展", 《热固性树脂》 * |
| 邓冲等: ""氧杂环丁烷/丙烯酸酯混杂体系的光固化性能研究"", 《影像科学与光化学》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108170003B (en) | A kind of elastic photosensitive resin for DLP 3D printing and preparation method thereof | |
| EP3686253B1 (en) | Curable clear ink composition, storing container, ink set, printing method, and cured material | |
| CN111349201B (en) | Resin composition for support material and method for producing stereolithography product | |
| CN110128773A (en) | A kind of photo-thermal dual curing 3D printing method and its product | |
| CN111349197B (en) | Dual-curing phase-separated continuous 3D printing high-precision photosensitive resin composition | |
| WO2018010490A1 (en) | Light cured transparent ink for 3d ink-jet printing and preparation method thereof | |
| CN111607289B (en) | A kind of dual-curing mechanism ultraviolet light curing inkjet printing ink and preparation method thereof | |
| WO2017185508A1 (en) | 3d ink-jet printing ink composition and ink set, and method for fabrication thereof | |
| WO2012042665A1 (en) | Adhesive composition, coating composition, primer using same, inkjet ink, adhesive method, and laminate | |
| US11667804B2 (en) | Photocurable transparent ink composition for three-dimensional molding and preparation method and application thereof | |
| CN106147381A (en) | The free radical that a kind of cure shrinkage is little/cation dual cure UV ink and preparation method thereof | |
| CN111989374B (en) | Inkjet ink composition, method for producing same, and image forming method | |
| CN107698722A (en) | Photosensitive resin of ultraviolet laser solidification and preparation method thereof | |
| WO2021217962A1 (en) | Bio-based uv-curable 3d printing resin and preparation method therefor | |
| CN113583188A (en) | High-weather-resistance high-toughness photocuring material for laser 3D printing and preparation method thereof | |
| CN102898878A (en) | Low-cost high-adhesive-force electron beam radiation curing paint and preparation method thereof | |
| CN113185646A (en) | Conductive 3D printing material and preparation method thereof | |
| CN104910689A (en) | Preparation method of pigment slurry for UV photocurable ink-jet printing | |
| EP3760679A1 (en) | Actinic ray curable inkjet ink composition | |
| CN113045715A (en) | Washable high-temperature-resistant conductive 3D printing photocuring material and printing process thereof | |
| CN112608429A (en) | Pretreatment dual-curing 3D printing resin and pretreatment method thereof | |
| CN111944358B (en) | Photoinitiated functional active pigment, ultraviolet curing ink, preparation method and application thereof | |
| CN102702848A (en) | Low-halogen rotation UV (Ultraviolet) environment-friendly ink and preparation method thereof | |
| EP2900773B1 (en) | Printing ink | |
| CN110527334B (en) | Vacuum visible light room temperature curing composite film based on carbon quantum dots and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210406 |
|
| RJ01 | Rejection of invention patent application after publication |