CN107236096B - Transparent SLA photosensitive resin composition - Google Patents
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- CN107236096B CN107236096B CN201710590607.3A CN201710590607A CN107236096B CN 107236096 B CN107236096 B CN 107236096B CN 201710590607 A CN201710590607 A CN 201710590607A CN 107236096 B CN107236096 B CN 107236096B
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- 239000011342 resin composition Substances 0.000 title claims abstract description 19
- 239000004417 polycarbonate Substances 0.000 claims abstract description 17
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000012745 toughening agent Substances 0.000 claims abstract description 8
- 150000003254 radicals Chemical class 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002091 cationic group Chemical group 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 150000002009 diols Chemical class 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- -1 glycidyl ester Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 4
- 239000012952 cationic photoinitiator Substances 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 229920005862 polyol Polymers 0.000 description 10
- 150000003077 polyols Chemical class 0.000 description 10
- 238000001723 curing Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 229920001610 polycaprolactone Polymers 0.000 description 4
- 239000004632 polycaprolactone Substances 0.000 description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- PODOEQVNFJSWIK-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethoxyphenyl)methanone Chemical compound COC1=CC(OC)=CC(OC)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 PODOEQVNFJSWIK-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000010998 test method Methods 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
-
- 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
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Photolithography (AREA)
- Epoxy Resins (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a transparent SLA photosensitive resin composition, which adopts polycarbonate dihydric alcohol as a modified toughening agent, the dosage of which is 3-15% of the total weight of the resin, and the transparent SLA photosensitive resin composition also comprises the following components in percentage by mass: 45-70% of cationic light curing component, 20-40% of free radical light curing component, 2-10% of cationic light initiator and 1-8% of free radical light initiator. The invention selects polycarbonate dihydric alcohol as the toughening agent of the system, can well balance water absorption, transparency and impact strength, and simultaneously does not influence the mechanical tensile strength of the system. The product has no bubble generation in the process, low water absorption rate, good toughness and transparency, and can well meet the requirements of customers on the construction of transparent products.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to a transparent SLA photosensitive resin composition.
[ background of the invention ]
The material for the photocuring rapid forming is liquid photocuring resin or liquid photosensitive resin, and mainly comprises oligomer, photoinitiator and diluent. In recent two years, photosensitive resins are being used in the emerging industry of 3D printing, which is favored and appreciated by the industry due to their excellent properties.
In the prior art, if the transparent SLA photosensitive resin is required to have good impact strength, generally, polyol is required to be added into a formula system as a toughening agent, and due to the problems of poor system compatibility, poor polyol hydrolysis resistance and the like, the introduction of polyester, polyether or polycaprolactone polyol generally causes the transparency of the system to be reduced, the water absorption to be increased, further causes the fogging of a workpiece, and the durability and the dimensional stability to be reduced.
The present invention is based on the above shortcomings of the products and the prior art.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provide a transparent SLA photosensitive resin composition which has good transparency and good mechanical tensile strength and impact strength and is suitable for 3D printing, photocuring coating or photoresist.
In order to achieve the purpose, the invention adopts the following technical scheme:
the transparent SLA photosensitive resin composition is characterized in that polycarbonate diol is adopted as a modified toughening agent, and the structural formula of the transparent SLA photosensitive resin composition is as follows:
wherein n is 1-7, wherein R1，R2The structural formula of (a) is selected from one of the following:
wherein m is 1-5;
the dosage of the polycarbonate diol is 3-15% of the total weight of the resin.
Compared with other types of polyols, such as polyester polyol, polycaprolactone polyol or polytetrahydrofuran polyol and the like, the polycarbonate diol has better hydrolysis resistance than ester groups in the molecular structure, and better acid-base resistance and ultraviolet resistance than ether bonds in polytetrahydrofuran polyol, and in SLA3D printing, the used cationic photoinitiator is a strong acid type substance, and the resin needs to work under the ultraviolet irradiation condition for a long time, so that the polyester, polycaprolactone or polytetrahydrofuran polyol for toughening modification can cause molecular chain breakage or other side reactions of the resin material due to ultraviolet irradiation, which is not beneficial to the stability maintenance of the performance of a product, while the hydrolysis of the ester groups under the strong acid condition can directly cause the increase of polar groups in the product, the water absorption of the product is increased, and the durability of the product is reduced, is not favorable for later application.
The transparent SLA photosensitive resin composition is characterized by comprising the following components in percentage by mass:
further, the transparent SLA photosensitive resin composition is characterized by comprising the following components in percentage by mass:
the cationic light-curing component in the invention is one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, alicyclic epoxy resin and vinyl ether monomers. One or more of bisphenol A glycidyl ether (NPEL-128), hydrogenated bisphenol A glycidyl ether (0575), 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate (TTA21), bis (7-oxabicyclo [4.1.0] 3-heptamethyl) adipate (TTA26) are preferred.
The free radical light curing component in the invention consists of acrylate monomers and prepolymers thereof. Preferably one or more of epoxy acrylate (CN104NS), trimethylolpropane triacrylate (SR351), polyethylene glycol 400 dimethacrylate (SR644), 1, 6-hexanediol diacrylate (SR238TFN), tricyclodecane dimethanol diacrylate (SR833S), (2) ethoxylated bisphenol A dimethacrylate (SR348L NS).
The cationic photoinitiator in the invention is preferably one or two of liquid hexafluoroantimonate (TR-PAG-20002) and propylene carbonate solution (CPI-101A) of 50% diphenyl- (4-phenylthio) phenyl sulfonium hexafluoroantimonate.
The free radical luminescence initiator in the invention is preferably one or more of 1-hydroxy-cyclohexyl-phenyl ketone (Irgacure184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (Daracur 1173), diphenyl (2,4, 6-trimethylbenzoyl) phosphorus oxide (Lucirin TPO).
The modified toughening agent in the invention is preferably polycarbonate diol BH-100 (wherein R1 and R2 are respectively shown in chemical formulas (1) and (3), and n is approximately equal to 3); polycarbonate diol PH-50(R1, R2 structures are respectively shown in chemical formulas (1) and (2), and n is approximately equal to 1); polycarbonate diol UHC-50-200(R1, R2 are shown in chemical formulas (1) and (5) respectively, wherein m is 2, and n is approximately equal to 4); polycarbonate diol UM-90(1/1) (wherein the structures of R1 and R2 are shown in chemical formulas (1) and (4), and n is approximately equal to 3) respectively.
The toughening agent used in the market at present is one of polyester polyol (CMA-1044) based on butanediol-adipic acid, polycaprolactone polyol (PCL303T) and polytetrahydrofuran polyol (PTMG 1000).
When the transparent SLA photosensitive resin composition is prepared, all the raw material components are mixed and stirred uniformly at room temperature (20-40 ℃).
Compared with the prior art, the invention has the following advantages:
the invention selects polycarbonate dihydric alcohol as the toughening agent of the system, can well balance water absorption, transparency and impact strength, and simultaneously does not influence the mechanical tensile strength of the system. The product has no bubble generation in the process, low water absorption rate, good toughness and transparency, and can well meet the requirements of customers on the construction of transparent products.
[ detailed description ] embodiments
The present invention will be described in more detail with reference to specific examples.
Table 1: percentage of each component of examples A-G
Table 2: percentage contents of each component of examples H to K and comparative examples 1 to 4
Examples A-K, comparative examples 1-4 were tested and the results are shown in Table 3, where: critical exposure energy EcAnd a curing depth DpThe test of (2):
using SLA3D printer, at a known laser power PLLaser scanning interval hsIn the case of different laser scanning rates VsPerforming single-layer scanning curing to obtain different thicknesses CdAccording to formula Cd＝Dpln[PL/(Vs*hs)]-DplnEcDrawing a corresponding straight line, wherein the curing depth D is determined from the slope and the inclination of the straight linepAnd critical exposure energy Ec。
Working fill scan rate:
using SLA3D printer at fixed power PLIn the case of 280mW, scan curing is performed, taking the maximum fill scan rate at which the liquid material can be cured and shaped, and can be removed for cleaning, as the working fill scan rate of the material. The index directly reflects the curing rate of the photosensitive material, wherein the higher the work filling scanning rate of the material is, the higher the forming efficiency of the material is, the time required for building the same workpiece in an SLA3D printer is greatly shortened, the work efficiency is greatly improved, and the time cost is reduced.
Testing of tensile strength and tensile modulus:
measured according to standard ASTM D638 using a computer tensile tester (Dongguan bond KJ-1065);
testing of Shore D hardness:
measured according to standard ASTM D2240 using a shore rubber durometer type D0-100 HD; notched impact strength test:
measured according to the standard ASTM D256 using a digital display pendulum impact tester (Dongguan key KJ-3090).
Testing of transparency:
the self-made test method comprises the steps of pouring 15 +/-0.2 g of liquid resin into a PP plastic cup, standing until no bubbles exist, placing the PP plastic cup into an ultraviolet post-curing box for irradiation for 20min, taking out the PP plastic cup, placing the PP plastic cup upside down, further irradiating for 20min, and comparing the PP plastic cup with a standard PMMA plate with the thickness of 1cm in transparency, wherein the transparency of the standard PMMA plate is set to be 5.
Table 3: comparative table of detailed test results of examples A to H and comparative examples 1 to 4
As can be seen from the performance indexes in Table 3, the SLA photosensitive resins of the examples A-K of the invention are superior to those of the comparative examples in transparency, and have low water absorption rate, so that the dimensional stability and the mechanical strength of a product can be effectively ensured to be maintained in the using process, the mechanical tensile strength and the toughness of the product are also excellent, the contradiction among the strength, the toughness, the water absorption rate and the like is well balanced, and the requirements of SLA3D on various performances of transparent resin materials in printing can be effectively met. In conclusion, compared with the prior art, the transparent photosensitive resin provided by the invention is greatly improved, and is worthy of popularization and application.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention shall fall within the protection scope defined by the claims of the present invention.
Claims (7)
1. The transparent SLA photosensitive resin composition is characterized in that polycarbonate diol is adopted as a modified toughening agent, and the structural formula of the transparent SLA photosensitive resin composition is as follows:
HO-R-(O-COO-R1-O-COO-R2)n-OH
wherein n is 1-7, R is R1Or R2Wherein R is1，R2The structural formula of (a) is selected from one of the following:
wherein m is 1-5,
the using amount of the polycarbonate diol is 3-15% of the total weight of the resin;
the polycarbonate diol is selected from the following group:
polycarbonate diol BH-100, wherein R1 and R2 have the structures shown in chemical formulas (1) and (3) respectively, n is approximately equal to 3,
polycarbonate diol PH-50, wherein R1 and R2 have the structures shown in chemical formulas (1) and (2), n is approximately equal to 1, and
polycarbonate diol UHC-50-200, wherein R1 and R2 have structural formulas shown in chemical formulas (1) and (5), respectively, wherein m is 2, and n is approximately equal to 4;
polycarbonate dihydric alcohol UM-90(1/1), wherein the structures of R1 and R2 are respectively shown in one of chemical formulas (1) and (4), and n is approximately equal to 3.
2. The transparent SLA photosensitive resin composition according to claim 1, characterized by comprising the following components in percentage by mass:
3. the transparent SLA photosensitive resin composition according to claim 2, characterized by comprising the following components in percentage by mass:
4. the transparent SLA photosensitive resin composition according to claim 2 or 3, wherein the cationic photocurable component is one or more of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, alicyclic epoxy resin and vinyl ether type monomers.
5. The transparent SLA photosensitive resin composition according to claim 2 or 3 wherein the free radical photocurable component consists of acrylate monomers and prepolymers thereof.
6. The transparent SLA photosensitive resin composition according to claim 2 or 3 wherein the cationic photoinitiator is selected from one or both of liquid hexafluoroantimonate and a 50% solution of diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate in propylene carbonate.
7. The transparent SLA photosensitive resin composition as defined in claims 2 or 3 wherein the free radical initiator is selected from one or more of 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl (2,4, 6-trimethylbenzoyl) phosphorous oxide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710590607.3A CN107236096B (en) | 2017-07-19 | 2017-07-19 | Transparent SLA photosensitive resin composition |
| PCT/CN2018/078545 WO2019015335A1 (en) | 2017-07-19 | 2018-03-09 | Transparent sla photosensitive resin composition |
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| CN201710590607.3A CN107236096B (en) | 2017-07-19 | 2017-07-19 | Transparent SLA photosensitive resin composition |
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| CN107236096B true CN107236096B (en) | 2020-05-26 |
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| CN107236096B (en) * | 2017-07-19 | 2020-05-26 | 中山大简科技有限公司 | Transparent SLA photosensitive resin composition |
| JP7227695B2 (en) | 2017-12-22 | 2023-02-22 | キヤノン株式会社 | Photocurable resin composition |
| CN109517340B (en) * | 2018-11-21 | 2021-03-23 | 中山大简科技有限公司 | Temperature-resistant transparent photosensitive resin for 3D printing |
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| US6379866B2 (en) * | 2000-03-31 | 2002-04-30 | Dsm Desotech Inc | Solid imaging compositions for preparing polypropylene-like articles |
| US6762002B2 (en) * | 1998-07-10 | 2004-07-13 | Dsm Desotech, Inc. | Solid imaging compositions for preparing polypropylene-like articles |
| US20050158660A1 (en) * | 2004-01-20 | 2005-07-21 | Dsm Desotech, Inc. | Solid imaging compositions for preparing polypropylene-like articles |
| US9676899B2 (en) * | 2006-05-01 | 2017-06-13 | Dsm Ip Assets B.V. | Radiation curable resin composition and rapid three dimensional imaging process using the same |
| WO2011075553A1 (en) * | 2009-12-17 | 2011-06-23 | Dsm Ip Assets, B.V. | Liquid radiation curable resins for additive fabrication comprising a triaryl sulfonium borate cationic photoinitiator |
| CN107236096B (en) * | 2017-07-19 | 2020-05-26 | 中山大简科技有限公司 | Transparent SLA photosensitive resin composition |
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|---|---|---|---|---|
| CN105399908A (en) * | 2015-12-23 | 2016-03-16 | 河南工程学院 | New UV laser curing rapid molding photosensitive resin and preparation method thereof |
| CN105713332A (en) * | 2016-04-14 | 2016-06-29 | 北京石油化工学院 | Ultraviolet-curable resin composite for laser 3D printing and preparation method of ultraviolet-curable resin composite |
| CN106749986A (en) * | 2016-12-12 | 2017-05-31 | 中山大简高分子材料有限公司 | A kind of epoxy phenolic resin composition for photocuring rapid prototyping |
| CN106749987A (en) * | 2016-12-12 | 2017-05-31 | 中山大简高分子材料有限公司 | It is a kind of for the SLA photosensitive resin compositions of 3D printing and its application |
Also Published As
| Publication number | Publication date |
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| WO2019015335A1 (en) | 2019-01-24 |
| CN107236096A (en) | 2017-10-10 |
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