CN107698722A - Photosensitive resin of ultraviolet laser solidification and preparation method thereof - Google Patents
Photosensitive resin of ultraviolet laser solidification and preparation method thereof Download PDFInfo
- Publication number
- CN107698722A CN107698722A CN201610639466.5A CN201610639466A CN107698722A CN 107698722 A CN107698722 A CN 107698722A CN 201610639466 A CN201610639466 A CN 201610639466A CN 107698722 A CN107698722 A CN 107698722A
- Authority
- CN
- China
- Prior art keywords
- photosensitive resin
- parts
- ultraviolet laser
- resin
- laser solidification
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 41
- 239000011347 resin Substances 0.000 title claims abstract description 41
- 238000007711 solidification Methods 0.000 title claims abstract description 20
- 230000008023 solidification Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- -1 acrylic ester Chemical class 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 12
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 150000003254 radicals Chemical class 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 229910000077 silane Inorganic materials 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 125000003566 oxetanyl group Chemical group 0.000 claims description 11
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 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 6
- 239000012955 diaryliodonium Substances 0.000 claims description 6
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical class C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- CWXZAJNUTOBAOI-UHFFFAOYSA-N 1-(2,3-dimethoxyphenyl)-2-hydroxy-2-phenylethanone Chemical compound COC1=CC=CC(C(=O)C(O)C=2C=CC=CC=2)=C1OC CWXZAJNUTOBAOI-UHFFFAOYSA-N 0.000 claims description 3
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 3
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004843 novolac epoxy resin Substances 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 150000002921 oxetanes Chemical class 0.000 claims description 3
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 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 1
- 239000000203 mixture Substances 0.000 claims 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 206010034960 Photophobia Diseases 0.000 abstract description 4
- 208000013469 light sensitivity Diseases 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical class CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical class CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 2
- UQRKXZOISAAYQQ-UHFFFAOYSA-N diphenylphosphorylformaldehyde Chemical group C=1C=CC=CC=1P(=O)(C=O)C1=CC=CC=C1 UQRKXZOISAAYQQ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000012663 cationic photopolymerization Methods 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 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
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- 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
- C08F283/10—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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
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)
- Materials For Photolithography (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of photosensitive resin of ultraviolet laser solidification and preparation method thereof, this photosensitive resin includes the raw material components of following parts by weight：1~5 part of 10~50 parts of acrylate, 5~30 parts of 10~50 parts of 5~40 parts of acrylic ester monomer, epoxy resin, the oxetane compound of hydroxyl, 1~10 part of cation-type photopolymerization initiators, 1 10 parts of free radical type Photoepolymerizationinitiater initiater and silane coupler.The raw materials by weight portion is matched and mixed by this method, and then heating stirring 30~150 minutes under 20~80 DEG C of temperature conditionss, make light yellow transparent liquid.This photosensitive resin effectively increases light sensitivity, reduces threshold exposure amount, improves the mechanical property and water resistance of printing part.
Description
Technical field
The present invention relates to a kind of photosensitive resin of ultraviolet laser solidification and preparation method thereof.
Background technology
Laser 3D printing can continuous printing speed three-dimensional body, it is mostly using special wax material, photosensitive resin, powdered gold
Category or plastics etc. can jointing material as printed material medium.Wherein photosensitive resin is generally made up of two parts, i.e. light trigger
And resin, resin are made up of prepolymer, diluent and a small amount of auxiliary agent.When the light trigger in photosensitive resin is irradiated by specific light source
When absorbing energy, free radical or cation can be produced, free radical or cation activate monomer and active copolymer, so as to occur
Cross-linking reaction and generate macromolecular solid compound.The light sensitivity of traditional photosensitive resin is poor, and threshold exposure amount is big, and threshold exposure amount is determined
Minimum energy when gel occurs for photosensitive resin is determined, therefore have impact on the curing rate and solidification effect of printing part, improved
Printing cost.
The content of the invention
The technical problems to be solved by the invention are photosensitive resins of ultraviolet laser solidification and preparation method thereof, this photosensitive tree
Fat effectively increases light sensitivity, reduces threshold exposure amount, improves the mechanical property and water resistance of printing part.
In order to solve the above technical problems, the photosensitive resin of ultraviolet laser solidification of the present invention includes the raw material of following parts by weight
Component：10~50 parts of 5~40 parts of acrylic ester monomer, epoxy resin, the oxa- of 10~50 parts of acrylate, hydroxyl
5~30 parts of cyclobutane compound, 1~10 part of cation-type photopolymerization initiators, free radical type Photoepolymerizationinitiater initiater 1-10 parts and
1~5 part of silane coupler.
Further, the acrylate is polyurethane acrylate resin, Epocryl, polyester
Acid ester resin, polyether acrylate resins or pure acrylate resin.
Further, the acrylic ester monomer of the hydroxyl refers to the simple function containing one or two hydroxyls in molecule
Degree, bifunctionality or three-functionality-degree acrylic ester monomer.
Further, the epoxy resin is cycloaliphatic epoxy resin, novolac epoxy resin, bisphenol A epoxide resin or it is mixed
Compound.
Further, the oxetane compound refers to a series of organic matters containing oxetane groups, including
Serial organic matter containing an oxetane groups, two oxetane groups or three oxetane groups.
Further, the cation-type photopolymerization initiators are Diaryl iodonium hexafluorophosphate, Diaryl iodonium hexafluoro
Stibate, triaryl sulphur hexafluorophosphate or triaryl sulphur hexafluoro antimonate.
Further, the free radical type Photoepolymerizationinitiater initiater is benzophenone, dimethoxybenzoin, 4- benzoyls -4-
Dimethyl diphenyl sulfide, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy cyclohexyl phenylketones, 2,4,6- trimethylbenzenes
It is formyl diphenyl phosphine oxide, double（2,4,6- trimethylbenzoyls）Phenyl phosphine oxide or 2- isopropyl thioxanthones.
Further, the silane coupler is 3- glycydoxies trimethoxy silane, 3- glycidol ethers
Epoxide propyl-triethoxysilicane, 3- methacryloxypropyl trimethoxy silanes or 2-（3,4- epoxy cyclohexanes）Ethyl
Trimethoxy silane.
A kind of preparation method of the photosensitive resin of the ultraviolet laser solidification, the raw materials by weight portion is matched mixed
Close, then heating stirring 30~150 minutes under 20~80 DEG C of temperature conditionss, make light yellow transparent liquid.
Photosensitive resin due to ultraviolet laser solidification of the present invention and preparation method thereof employs above-mentioned technical proposal, i.e. this photosensitive tree
Fat includes the raw material components of following parts by weight：The acrylic ester monomer 5~40 of 10~50 parts of acrylate, hydroxyl
Part, 10~50 parts of epoxy resin, 5~30 parts of oxetane compound, 1~10 part of cation-type photopolymerization initiators, freedom
1~5 part of fundamental mode Photoepolymerizationinitiater initiater 1-10 parts and silane coupler.The raw materials by weight portion is matched and mixed by this method,
Then heating stirring 30~150 minutes under 20~80 DEG C of temperature conditionss, make light yellow transparent liquid.This photosensitive resin
Light sensitivity is effectively increased, reduces threshold exposure amount, improves the mechanical property and water resistance of printing part.
Embodiment
The photosensitive resin of ultraviolet laser solidification of the present invention includes the raw material components of following parts by weight：Acrylate 10
~50 parts, 10~50 parts of 5~40 parts of acrylic ester monomer, epoxy resin, the oxetane compound 5~30 of hydroxyl
1~5 part of part, 1~10 part of cation-type photopolymerization initiators, free radical type Photoepolymerizationinitiater initiater 1-10 parts and silane coupler.
Preferably, the acrylate is polyurethane acrylate resin, Epocryl, polyester
Acid ester resin, polyether acrylate resins or pure acrylate resin.
Preferably, the acrylic ester monomer of the hydroxyl refers to the simple function containing one or two hydroxyls in molecule
Degree, bifunctionality or three-functionality-degree acrylic ester monomer.
Preferably, the epoxy resin is cycloaliphatic epoxy resin, novolac epoxy resin, bisphenol A epoxide resin or it is mixed
Compound.
Preferably, the oxetane compound refers to a series of organic matters containing oxetane groups, including
Serial organic matter containing an oxetane groups, two oxetane groups or three oxetane groups.
Preferably, the cation-type photopolymerization initiators are Diaryl iodonium hexafluorophosphate, Diaryl iodonium hexafluoro
Stibate, triaryl sulphur hexafluorophosphate or triaryl sulphur hexafluoro antimonate.
Preferably, the free radical type Photoepolymerizationinitiater initiater is benzophenone, dimethoxybenzoin, 4- benzoyls -4-
Dimethyl diphenyl sulfide, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy cyclohexyl phenylketones, 2,4,6- trimethylbenzenes
It is formyl diphenyl phosphine oxide, double（2,4,6- trimethylbenzoyls）Phenyl phosphine oxide or 2- isopropyl thioxanthones.
Preferably, the silane coupler is 3- glycydoxies trimethoxy silane, 3- glycidol ethers
Epoxide propyl-triethoxysilicane, 3- methacryloxypropyl trimethoxy silanes or 2-（3,4- epoxy cyclohexanes）Ethyl
Trimethoxy silane.
A kind of preparation method of the photosensitive resin of the ultraviolet laser solidification, the raw materials by weight portion is matched mixed
Close, then heating stirring 30~150 minutes under 20~80 DEG C of temperature conditionss, make light yellow transparent liquid.
The mechanism of cationic photopolymerization is that cation-type photopolymerization initiators produce super strong proton under the irradiation of ultraviolet light
Acid, trigger monomer polymerization, in this process, hydroxyl can accelerate the polymerization speed of cation as chain-transferring agent.Usual light
Hydroxyl donor is typically used as using polycaprolactone polyol and PolyTHF ethoxylated polyhydric alcohol etc. in quick resin, but it is this kind of polynary
Alcohol is all not involved in reacting, and all has an impact to the mechanical strength and water resistance for finally printing model.It is used in this photosensitive resin
The acrylic ester monomer of hydroxyl not only provides the hydroxyl for promoting cationic polymerization speed, and can participate in free radical system
Curing cross-linking reaction, the final mechanical strength and water resistance for printing product can be improved.
Embodiment one
1. in 5000 milliliters of glass there-necked flasks equipped with agitator and condenser pipe, 410 grams of hydroxyethyl methacrylate of addition, 3,
Double sub- first base ﹞ -600 grams of the bis- ﹝ 3- second base ﹞ oxetanes of 3- ﹝ epoxides, 700 grams of polyurethane acrylic resin, aliphatic ring oxygen tree
1000 grams of fat, 100 grams of 1- hydroxy cyclohexyl phenylketones, 130 grams of triaryl sulphur hexafluoro antimonate, 3- methacryloxies third
60 grams of base trimethoxy silicon.
2. being heated to 50 DEG C, stir 60 minutes, make pale yellow transparent uniform liquid, this liquid is what is prepared
A kind of photosensitive resin.Measure its threshold exposure amount ECFor 14.3mj/cm2。
3. test block is made using the Lite300 type SLA3D printers of Lian Tai companies production, then in the milliwatt of power 500
Ultraviolet case solidify afterwards 90 minutes, measure the warp factor CF of test block（6）=0.01, CF（11）=0.02, tensile strength
30.2MPa, elongation at break 15.1%, impact strength 14.3J/m；Their 24 hours water absorption rates are measured less than 0.5%.
Embodiment two
1. in 5000 milliliters of glass there-necked flasks equipped with agitator and condenser pipe, 410 grams of pentaerythritol triacrylate is added,
3,3- 600 grams of ﹝ epoxide Shuan Ya Jia Ji ﹞-Shuan ﹝ 3- Yi Ji ﹞ oxetanes, 700 grams of polyurethane acrylic resin, alicyclic epoxy
1000 grams of resin, 100 grams of 1- hydroxy cyclohexyl phenylketones, 130 grams of triaryl sulphur hexafluoro antimonate, 3- methacryloxies
60 grams of propyl trimethoxy silicon.
2. being heated to 50 DEG C, stir 60 minutes, make pale yellow transparent uniform liquid, this liquid is what is prepared
A kind of photosensitive resin.Measure its threshold exposure amount ECFor 13.1mj/cm2。
3. test block is made using the Lite300 type SLA3D printers of Lian Tai companies production, then in the milliwatt of power 500
Ultraviolet case solidify afterwards 90 minutes, measure their warp factor CF（6）=0.01, CF（11）=0.03, tensile strength
28.7MPa, elongation at break 11.1%, impact strength 12.8J/m, 24 hours water absorption rates are less than 0.5%.
Claims (9)
- A kind of 1. photosensitive resin of ultraviolet laser solidification, it is characterised in that：This photosensitive resin includes the raw material of following parts by weight Component：10~50 parts of 5~40 parts of acrylic ester monomer, epoxy resin, the oxa- of 10~50 parts of acrylate, hydroxyl 5~30 parts of cyclobutane compound, 1~10 part of cation-type photopolymerization initiators, free radical type Photoepolymerizationinitiater initiater 1-10 parts and 1~5 part of silane coupler.
- 2. the photosensitive resin of ultraviolet laser solidification according to claim 1, it is characterised in that：The acrylate is Polyurethane acrylate resin, Epocryl, polyester acrylate resin, polyether acrylate resins or pure propylene Acid ester resin.
- 3. the photosensitive resin of ultraviolet laser solidification according to claim 1, it is characterised in that：The acrylic acid of the hydroxyl Esters monomer refers to single functionality, bifunctionality or three-functionality-degree esters of acrylic acid list containing one or two hydroxyls in molecule Body.
- 4. the photosensitive resin of ultraviolet laser solidification according to claim 1, it is characterised in that：The epoxy resin is alicyclic ring Race's epoxy resin, novolac epoxy resin, bisphenol A epoxide resin or its mixture.
- 5. the photosensitive resin of ultraviolet laser solidification according to claim 1, it is characterised in that：The oxetanes chemical combination Thing refers to a series of organic matters containing oxetane groups, including contains an oxetane groups, two oxa- rings The serial organic matter of butane group or three oxetane groups.
- 6. the photosensitive resin of ultraviolet laser solidification according to claim 1, it is characterised in that：The cation-type photopolymerization Initiator is Diaryl iodonium hexafluorophosphate, Diaryl iodonium hexafluoro antimonate, triaryl sulphur hexafluorophosphate or three virtues Base sulphur hexafluoro antimonate.
- 7. the photosensitive resin of ultraviolet laser solidification according to claim 1, it is characterised in that：The free radical type photopolymerization Initiator is benzophenone, dimethoxybenzoin, 4- benzoyl -4- dimethyl diphenyl sulfides, 2- hydroxy-2-methyl -1- benzene It is base -1- acetone, 1- hydroxy cyclohexyl phenylketones, 2,4,6- trimethylbenzoyls diphenyl phosphine oxide, double（2,4,6- trimethylbenzenes Formyl）Phenyl phosphine oxide or 2- isopropyl thioxanthones.
- 8. the photosensitive resin of ultraviolet laser solidification according to claim 1, it is characterised in that：The silane coupler is 3- Glycydoxy trimethoxy silane, 3- glycydoxies triethoxysilane, 3- methacryls Epoxide propyl trimethoxy silicane or 2-（3,4- epoxy cyclohexanes）Ethyl trimethoxy silane.
- A kind of 9. preparation method of the photosensitive resin of any one of claim 1 to 8 ultraviolet laser solidification, it is characterised in that： The raw materials by weight portion is matched and mixed, then heating stirring 30~150 minutes under 20~80 DEG C of temperature conditionss, are allowed to As light yellow transparent liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610639466.5A CN107698722A (en) | 2016-08-08 | 2016-08-08 | Photosensitive resin of ultraviolet laser solidification and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610639466.5A CN107698722A (en) | 2016-08-08 | 2016-08-08 | Photosensitive resin of ultraviolet laser solidification and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107698722A true CN107698722A (en) | 2018-02-16 |
Family
ID=61168265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610639466.5A Pending CN107698722A (en) | 2016-08-08 | 2016-08-08 | Photosensitive resin of ultraviolet laser solidification and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107698722A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108841345A (en) * | 2018-07-09 | 2018-11-20 | 烟台德邦科技有限公司 | One specific admixture solidifies photic blackening acrylate adhesive |
| CN111748312A (en) * | 2020-06-22 | 2020-10-09 | 江苏泰特尔新材料科技有限公司 | Cationic free radical dual-curing adhesive and preparation method thereof |
| CN113185646A (en) * | 2021-06-12 | 2021-07-30 | 湖南创瑾科技有限公司 | Conductive 3D printing material and preparation method thereof |
| CN113248636A (en) * | 2021-06-21 | 2021-08-13 | 贵州师范学院 | Thioxanthone visible light initiator, preparation method and application |
| CN113416380A (en) * | 2021-05-21 | 2021-09-21 | 东莞爱的合成材料科技有限公司 | Resin composition and preparation method and application thereof |
| CN113462200A (en) * | 2021-07-01 | 2021-10-01 | 本时智能技术发展(上海)有限公司 | Amino polymerization-resistant modified heat-conducting particle and preparation method thereof |
| CN113754441A (en) * | 2021-03-15 | 2021-12-07 | 山东理工大学 | Photosensitive resin and preparation method and application thereof |
| CN114096612A (en) * | 2020-01-27 | 2022-02-25 | 日立能源瑞士股份公司 | Photoradiation curable epoxy resin for electrical parts |
| CN115537124A (en) * | 2022-09-28 | 2022-12-30 | 新纶电子材料(常州)有限公司 | Post-curable optical adhesive, OCA (optical clear adhesive) and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102436145A (en) * | 2011-09-01 | 2012-05-02 | 南昌大学 | Stereo lithography rapid prototyping photosensitive resin and preparation method thereof |
| CN105175651A (en) * | 2015-09-21 | 2015-12-23 | 江苏科技大学 | Three-dimensional printing photosensitive resin material containing solid rubber and preparation method |
| CN107109091A (en) * | 2014-12-29 | 2017-08-29 | 三星电子株式会社 | For the ink composite of 3D printing, 3D printer and the method for controlling it |
-
2016
- 2016-08-08 CN CN201610639466.5A patent/CN107698722A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102436145A (en) * | 2011-09-01 | 2012-05-02 | 南昌大学 | Stereo lithography rapid prototyping photosensitive resin and preparation method thereof |
| CN107109091A (en) * | 2014-12-29 | 2017-08-29 | 三星电子株式会社 | For the ink composite of 3D printing, 3D printer and the method for controlling it |
| CN105175651A (en) * | 2015-09-21 | 2015-12-23 | 江苏科技大学 | Three-dimensional printing photosensitive resin material containing solid rubber and preparation method |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108841345A (en) * | 2018-07-09 | 2018-11-20 | 烟台德邦科技有限公司 | One specific admixture solidifies photic blackening acrylate adhesive |
| CN114096612A (en) * | 2020-01-27 | 2022-02-25 | 日立能源瑞士股份公司 | Photoradiation curable epoxy resin for electrical parts |
| CN111748312A (en) * | 2020-06-22 | 2020-10-09 | 江苏泰特尔新材料科技有限公司 | Cationic free radical dual-curing adhesive and preparation method thereof |
| CN111748312B (en) * | 2020-06-22 | 2022-04-29 | 江苏泰特尔新材料科技股份有限公司 | Cationic free radical dual-curing adhesive and preparation method thereof |
| CN113754441A (en) * | 2021-03-15 | 2021-12-07 | 山东理工大学 | Photosensitive resin and preparation method and application thereof |
| CN113754441B (en) * | 2021-03-15 | 2023-02-17 | 山东理工大学 | Photosensitive resin and preparation method and application thereof |
| CN113416380A (en) * | 2021-05-21 | 2021-09-21 | 东莞爱的合成材料科技有限公司 | Resin composition and preparation method and application thereof |
| CN113185646A (en) * | 2021-06-12 | 2021-07-30 | 湖南创瑾科技有限公司 | Conductive 3D printing material and preparation method thereof |
| CN113248636A (en) * | 2021-06-21 | 2021-08-13 | 贵州师范学院 | Thioxanthone visible light initiator, preparation method and application |
| CN113462200A (en) * | 2021-07-01 | 2021-10-01 | 本时智能技术发展(上海)有限公司 | Amino polymerization-resistant modified heat-conducting particle and preparation method thereof |
| CN115537124A (en) * | 2022-09-28 | 2022-12-30 | 新纶电子材料(常州)有限公司 | Post-curable optical adhesive, OCA (optical clear adhesive) and preparation method thereof |
| CN115537124B (en) * | 2022-09-28 | 2024-04-05 | 新纶电子材料(常州)有限公司 | Post-curable optical adhesive, OCA optical adhesive and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107698722A (en) | Photosensitive resin of ultraviolet laser solidification and preparation method thereof | |
| CN108170003B (en) | Elastic photosensitive resin for DLP 3D printing and preparation method thereof | |
| CN104031588B (en) | Glue bond material and preparation method thereof | |
| CN104559140B (en) | 3D printing-based photo-curing material and preparation method thereof | |
| CN104311783A (en) | Unsaturated hyperbranched polyurethane prepolymer as well as preparation method and application thereof | |
| CN100387631C (en) | Novel resin-curing process enabling the actinic radiation cure of resins containing shieldings against actinic radiations, composition for the process, moldings and molding process | |
| CN105399908B (en) | A kind of ultraviolet laser solidification rapid shaping photosensitive resin and preparation method thereof | |
| CN105399905B (en) | A kind of photocurable three-dimensional printing materials and preparation method thereof | |
| CN107698718A (en) | Photosensitive resin for laser 3D printing and preparation method thereof | |
| CN112080241B (en) | Photo-curing adhesive and preparation method and application thereof | |
| CN106317898A (en) | Photocured organosilicone elastomer and preparation method and application thereof | |
| CN108948280A (en) | A kind of double cured 3D printing resin combinations of optical and thermal | |
| CN112126402A (en) | Photo-curing adhesive and preparation method and application thereof | |
| CN105348414B (en) | Method and composition used for realizing deep cationic photopolymerization | |
| CN105462134A (en) | Multi-curing enhanced 3D printing material and manufacturing method thereof | |
| CN104403268A (en) | Ultraviolet-curable resin composition and fiber reinforced resin-based composite material thereof | |
| CN104761994A (en) | Preparation method of photocuring organic silicon modified epoxy resin paint film | |
| CN105131581A (en) | Photocurable liquid resin composition for three-dimensional molding and molded object obtained by photocuring same | |
| CN106010398A (en) | Cationic ultraviolet-deep-curing adhesive and preparation method thereof | |
| CN103265704B (en) | A kind of organosilicon-modified acrylic UV-Curing Waterborne Resin and preparation method thereof | |
| CN109535330A (en) | A kind of DLP 3D printing photosensitive resin | |
| CN105237689A (en) | Digital light procession photocuring material and preparing method thereof | |
| CN109438631A (en) | A kind of high-precision and high heat distortion temperature stereolithography 3D printing photosensitive resin and preparation method thereof | |
| CN102952257A (en) | Method for preparing stereolithography rapid-prototyping photosensitive resin by adopting 1,4-cyclohexanedimethanol diglycidyl ether diacrylate as prepolymer | |
| CN104448715A (en) | Photo-curing material for injection type 3D printer |
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: 20180216 |
|
| RJ01 | Rejection of invention patent application after publication |