CN102385250A - Ultraviolet laser solidification rapid-prototyping photosensitive resin and manufacture method thereof - Google Patents
Ultraviolet laser solidification rapid-prototyping photosensitive resin and manufacture method thereof Download PDFInfo
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- CN102385250A CN102385250A CN2011101776764A CN201110177676A CN102385250A CN 102385250 A CN102385250 A CN 102385250A CN 2011101776764 A CN2011101776764 A CN 2011101776764A CN 201110177676 A CN201110177676 A CN 201110177676A CN 102385250 A CN102385250 A CN 102385250A
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Abstract
The invention discloses an ultraviolet laser solidification rapid-prototyping photosensitive resin and a manufacture method thereof. The ultraviolet laser solidification rapid-prototyping photosensitive resin comprises the following components in mass ratio: 5-80% of epoxy resin, 0-65% of oxetane compound, 1-12% of cationic initiator, 1-40% of hydroxy organic compound, 0-55% of unsaturated oligmer containing C-C double bonds, 0-35% of unsaturated monomer containing C-C double bonds, 0-20% of glycidyl ether or epoxy diluent with low molecular weight and 0-10% of free redical type photopolymerization initiator. The manufacture method comprises the following steps: mixing the raw materials in the mass ratio, heating at 20-80DEG C, and stirring for 5-120 minutes to obtain transparent faint yellow uniform liquid. The photosensitive resin disclosed by the invention has good photosensitiveness, and the critical exposure Ec is less than 15mJ/cm<2>; a formed part has high precision; the camber factor CF(6) of the formed part is between-0.01 and 0.01; and the camber factor CF (11) is between -0.03 and 0.03. The photosensitive resin disclosed by the invention can be directly manufactured into any part with complex shape, high precision and low cost.
Description
Technical field
The invention belongs to rapid shaping and make the field, relate to rapid-result type material of Ultra-Violet Laser quick solidifying and preparation method.
Background technology
Rapid shaping is quick a design and forming technique that grows up in the later stage eighties 20th century.The core concept of rapid shaping processing is the discrete moulding of piling up.That is: go out the Computerized three-dimensional curved surface or the solid model of required part by the CAD software design: three-dimensional model is separated into a series of orderly two-dimentional synusia (custom is called layering) along certain orientation (be generally Z to); According to every layer of profile information, carry out process planning, select machined parameters, generate numerical control code automatically: make-up machine is made the series of layers sheet and automatically it is linked up, and obtains three-dimensional physical entity.Rapid shaping technique combines the achievement in research of science and technology such as laser, computer-aided design (CAD) and manufacturing, photochemistry, new material, does not need any machining equipment can make the object of complicated shape (drip molding, or title part) quickly and accurately.Quick shaping process commonly used has: Ultra-Violet Laser solidifies rapid shaping (or being called the stereolithography rapid shaping), selective laser sintering rapid forming, and the fuse deposition rapid forming, laminated solid body is made rapid shaping etc.Wherein Ultra-Violet Laser curing rapid shaping is with Ultra-Violet Laser shape point by point scanning by two-dimensional section on the resin liquid level; Make resin solidification; Resin after the curing just forms an X-Y scheme, and scanning is so successively solidified; Finally can obtain complete 3D solid (drip molding, or title part).In Ultra-Violet Laser solidified rapid shaping, photosensitive resin was the basis, the precision that the quality of photosensitive resin will determine drip molding with and mechanical property and thermal behavior.
Abroad, the photosensitive resin that is applied to Ultra-Violet Laser curing rapid shaping develops into now, is broadly divided into the three generations.Early stage commercial photosensitive resin refers to that promptly the photosensitive resin of the 1980s and earlier 1990s all is with the free radical type photosensitive resin as prepolymer such as epoxy acrylate or urethane acrylate, like 5081,5131 and 5149 types of Ciba-Geigy Cibatool company research and development and 2100,2110,3100 and 3110 types of Dupont company research and development etc.Advantages such as it is cheap that though this type photosensitive resin has, and solidification rate is fast, because cure shrinkage is serious, the drip molding warpage is obvious, and precision is difficult to meet the demands, and is finally still replaced by the photosensitive resin of a new generation.The rapid-result type photosensitive resin prepolymer of the commercial Ultra-Violet Laser quick solidifying of the second generation is main with epoxy resin mainly, and acrylic ester is auxilliary, and it belongs to the photosensitive resin of free radical-cation type initiated polymerization.Compare characteristics such as it has, and viscosity is low, drip molding precision height with first generation esters of acrylic acid photosensitive resin.Solidify the development and the popularization of rapid shaping technique along with Ultra-Violet Laser; People are also increasingly high to the requirement of photosensitive resin; Especially along with the direction of rapid shaping technique to direct finished parts and mould develops, the finally bigger challenge of the rapid-result profile of Ultra-Violet Laser quick solidifying.Like this, just, the rapid-result type photosensitive resin of the third generation Ultra-Violet Laser quick solidifying that has been born.And precision is high, the fabulous photosensitive resin that can directly use as functor of pliability is wherein one type; For example, the Somos11120 type photosensitive resin of U.S. DSM Somos company, its drip molding pliability is fabulous; Can directly use, and embrittlement does not take place as assembly parts.The Somos11120 type photosensitive resin of this high precision and high-flexibility is to global marketing, its selling price be per kilogram up to 1500 yuans, its technology of preparing is very secret.
At home, in recent ten years, there are many universities and scientific research institute, place to carry out the research of the rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying, obtained some achievements.But research is not also not deeply, so that the photosensitive resin of the photosensitive resin of present U.S. DSM Somos company and Huntsman company still the market of the rapid-result type photosensitive resin of China's Ultra-Violet Laser quick solidifying with the price fixing of costliness.At present, domestic having two parts of patents of invention aspect the research of the rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying.Guangzhou Inst. of Machinery Science Haitao Liu, Zhong Hanrong and Xue Jidong have proposed " a kind of stereolithography rapid prototyping photosensitive resin ", have applied for patent, and the number of applying for a patent is CN200910040526.1.This stereolithography rapid prototyping photosensitive resin is characterized in that: comprise following quality proportion raw material component: epoxy resin 30-80%, acrylic ester 10-35%, radical initiator 1.0-5.0%, cationic initiating agent 1.0-8.0% and thinning agent 5-40%.At the epoxy resin described in this part patent is novalac epoxy or the cycloaliphatic epoxy resin that has oneself ring; The described cycloaliphatic epoxy resin that has own ring is 3,4-epoxycyclohexyl formic acid-3
', 4
'-epoxycyclohexyl methyl esters; Described acrylic ester is pentaerythritol triacrylate, dipentaerythritol monohydroxy five acrylic ester, bisphenol A epoxy acrylate, phenolic aldehyde epoxy acrylic or two or more potpourri in them; Described thinning agent is epoxy resin diluent, acrylic ester thinning agent or their potpourri; Described epoxy resin diluent is a trihydroxymethylpropanyltri diglycidyl ether, and described acrylic ester thinning agent is a trimethylolpropane triacrylate.The king of Zhejiang Polytechnical University sea moral, Malaysian is outstanding, and Sun Xingping waits to have proposed " a kind of UV curing photosensitive resin for rapid moulding injection mold ", has applied for patent, and the number of applying for a patent is CN200910095846.7.This invention provides a kind of UV curing photosensitive resin for rapid moulding injection mold; Raw material by the quality proportioning is following is processed: active component comprises: oligomer A, oligomer B and 1: 1: 1 potpourri of epoxy resin 70～80% (to account for active component gross mass number percent, down together); Reactive diluent, 20～30%; Auxiliary agent comprises: foam-breaking agent 0.1～1.0%; Levelling agent 0.1～1.0%; Adhesion promoter, 0.01～5%; Radical initiator, 1～10%; Cationic initiator, 1～10%.Said oligomer A is E-44 propylene oxide acid monoester or E-51 propylene oxide acid monoester; Said oligomer B is one of following: epoxy acrylate, urethane acrylate, polyester acrylate; Said epoxy resin is E-44 epoxy resin or E-51 epoxy resin; Said reactive diluent is bifunctional monomer or trifunctional monomer.For application number is the CN200910040526.1 patent; This patent is all considered comprehensive inadequately in epoxy resin and acrylic ester or the selection at thinning agent; For example; Oxetanes is the same prepolymer that can be used as photosensitive resin with epoxy resin just, and just the dilution effect than epoxide resin type thinning agent and acrylic ester type thinning agent is good usually as its dilution effect of thinning agent for vinyl ether, does not mention vinyl ether and in this part patent, both mentioned oxetanes.With regard to application number is the CN200910095846.7 patent; It has only considered E-44 epoxy resin or E-51 epoxy resin on the epoxy resin breed selection, selects the active higher cycloaliphatic epoxy resin of cation type ultraviolet photo-curing (or claiming alicyclic epoxide compound) and ignored.Therefore, this part patent also seems a bit not enough.
Summary of the invention
The objective of the invention is to overcome the weak point of above-mentioned prior art, the preparation method of the rapid-result type photosensitive resin of high precision Ultra-Violet Laser quick solidifying is provided.
The present invention realizes through following technical scheme.
The rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying of the present invention is made up of following raw material by the quality proportioning:
5～80% epoxy resin
0～65% oxetane compound
1～12% cationic initiating agent
1～40% hydroxyl organic compound
0～55% unsaturated oligomer that contains carbon-to-carbon double bond or title prepolymer
0～35% the unsaturated monomer that contains carbon-to-carbon double bond
0～20% low-molecular-weight glycidol ether or title epoxide diluent
0～10% free radical type Photoepolymerizationinitiater initiater.
Epoxy resin according to the invention comprises phenol aldehyde type epoxy resin, bisphenol A type epoxy resin, cycloaliphatic epoxy resin or claim alicyclic epoxide compound etc., or their potpourris of several kinds.Preferably, select cycloaliphatic epoxy resin, for example, 3,4-epoxycyclohexyl formic acid-3
', 4
'-epoxycyclohexyl methyl esters.
Oxetane compound of the present invention is meant a series of organism that contain oxetane groups; It comprises contains an oxetane groups; Two oxetane groups, the serial organism of three oxetane groups and a plurality of oxetane groups.Preferably, select to contain two oxetane groups, the serial organism of three oxetane groups and a plurality of oxetane groups.
Cationic initiating agent of the present invention comprises salt compounded of iodine and sulfonium salt, wherein mainly is meant diaryl iodine hexafluorophosphate, diaryl iodine hexafluoro arsenate, diaryl iodine hexafluoro antimonate and triaryl matte hexafluorophosphate, triaryl matte hexafluoro arsenate, triaryl matte hexafluoro antimonate etc.Preferably, select triaryl matte hexafluorophosphate, triaryl matte hexafluoro arsenate and triaryl matte hexafluoro antimonate.
Hydroxyl organic compound of the present invention comprises the organism that contains an oh group, the organism of two oh groups, the organism of three oh groups and the organism of a plurality of oh groups.Preferably, select polyol compound, for example, polycaprolactone dibasic alcohol and polycaprolactone trihydroxy alcohol.
The unsaturated oligomer that contains carbon-to-carbon double bond of the present invention comprises epoxy acrylate, urethane acrylate, polyester acrylate, amino acrylates, polyether acrylate, pure acrylic acid ester and organosilicon, Organic fluoride acrylic ester etc.Preferably, select epoxy acrylate, mainly be meant bisphenol-a epoxy acrylate.
The unsaturated monomer that contains carbon-to-carbon double bond of the present invention comprises acrylate monomer and vinyl ether monomers.Preferably, select to contain in the molecule acrylate monomer or the vinyl ether monomers of two or more carbon-to-carbon double bonds, perhaps their mix monomer.
The low-molecular-weight glycidol ether that contains two or more epoxide groups in low-molecular-weight glycidol ether of the present invention or the preferred molecule of title epoxide diluent.For example, ethylene glycol diglycidylether, tripropyleneglycol diglycidyl ether and 1,4-butanediol diglycidyl ether etc.
Free radical type Photoepolymerizationinitiater initiater of the present invention comprises can cause the free radical type initiating agent that all unsaturated monomers that contain carbon-to-carbon double bond carry out polymerization.Preferably, select benzophenone, styrax dimethyl ether, chlorinated diphenyl ketone, 4-benzoyl-4
'-dimethyl diphenyl sulfide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy cyclohexyl phenylketone and 2,4-diethyl thioxanthone, perhaps both or both above potpourri in them.
The present invention also provides the preparation method of the rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying, is that said material component is mixed by described quality proportioning; Then, heating, stirring promptly 20～80 ℃ of temperature, were stirred 5～120 minutes, made it to become the transparent faint yellow uniform liquid.
Ultimate principle of the present invention is following.
Has less shrinkability when solidifying for the rapid-result type photosensitive resin of the Ultra-Violet Laser quick solidifying that makes preparation; Product has higher precision, and the present invention adopts epoxy resin, oxetanes or their potpourri as much as possible for the prepolymer of photosensitive resin, uses acrylic ester, vinyl ether less as far as possible; Because the polymerization of epoxy resin, oxetanes is ring-opening polymerization; Shrink for a short time, and the polymerization of the polymerization of acrylic ester, vinyl ether to be carbon-to-carbon double bond fracture become singly-bound is shunk greatly.Yet; For the photosensitive resin that makes preparation has better photosensitivity; Need adopt acrylic ester, vinyl ether as raw material as much as possible; Use epoxy resin, oxetanes as raw material less because acrylic ester, vinyl ether under UV-irradiation its solidification rate faster than the solidification rate of epoxy resin, oxetanes.In order to make photosensitive resin can keep high precision property when the product and to take into account the photosensitivity of photosensitive resin, should adopt epoxy resin, oxetanes to adopt acrylic ester, vinyl ether again during the preparation photosensitive resin, good this balance of GPRS.In order to prepare the rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying, the present invention also selects ultraviolet initiator.Initiating agent preferably selects to comprise the free radical type initiating agent and the cationic initiating agent that causes epoxy resin, oxetanes and vinyl ether polymerization of initiating methacrylates polymerization.When selecting initiating agent, to notice considering that initiating agent has response preferably to the specific wavelength ultraviolet light that ultraviolet laser sent, promptly the 355nm ultraviolet light had response preferably.
The present invention has following beneficial effect.
With respect to commercialization photosensitive resin in the past, its principal feature of photosensitive resin of the present invention's preparation is: at first, the photosensitivity of photosensitive resin is good, its critical exposure E
cLess than 15mJ/cm
2Secondly, the precision of formation of parts is high, and the warp factor CF of formation of parts (6) is in ± 0.01 scope, and CF (11) is in ± 0.03 scope.
Adopt the photosensitive resin of the present invention's preparation can directly produce any complicated shape, have a high-precision part; And the preparation cost valency of this photosensitive resin is about 300 yuan an of per kilogram, far below the selling price (about 1500 yuans of per kilogram) of the photosensitive resin of DSM Somos company and Huntsman company.
Embodiment
Below in conjunction with embodiment, the present invention is done detailed description further, but implementation of the present invention is not limited thereto.
Embodiment 1.
1. in the special 5000 milliliters glass there-necked flask of stirrer and condenser pipe is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-cyclohexyl methyl esters 1300 grams, 3,3-[oxygen base dimethylene]-two [3-ethyl] oxetanes 400 grams; Bisphenol-a epoxy acrylate (EA-612) 500 grams, polycaprolactone trihydroxy alcohol (Polyol0301) 330 grams, trimethylolpropane triacrylate 100 grams; 1; 4-cyclohexyl dimethanol divinyl ether 100 grams, styrax dimethyl ether 100 grams, triaryl matte hexafluoro antimonate 170 grams.
2. be heated to 50 ℃, stirred 30 minutes, make it to become the transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.Record its critical exposure E
cBe 11.2 mJ/cm
2, method of testing be adopt " Zhao Yi. the experimental study of photosensitive resin characteristic [J] in the laser fast forming. polymer material science and engineering, 2004,20 (1): 184-186 " institute's reported method.
3. the SLA-3500 type Ultra-Violet Laser that utilizes 3D Systems company to produce has solidified the rapid shaping equipment making some test blocks then, are in the 500 milliwatt ultraviolet casees at power, and these test blocks were solidified 90 minutes in the back.Record their warp factor CF (6)=0.01, CF (11)=0.02.For the rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying make the precision evaluation standard of part existing popular be the warp factor evaluation method, what its method adopted is the method for being formulated in second international quick shaping meeting holding in 1991.
Embodiment 2.
1. in the special 5000 milliliters glass there-necked flask of stirrer and condenser pipe is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-cyclohexyl methyl esters 1200 grams, 1, two [(3-ethyl-3-oxygen methylene oxetanes) methyl] benzene 400 grams of 4-; Bisphenol A type epoxy resin (E-51) 100 grams, pentaerythritol triacrylate 600 grams, polycaprolactone dibasic alcohol (Polyol0201) 320 grams; 1; 4-butanediol diglycidyl ether 100 grams, 2-hydroxy-2-methyl-1-phenyl-1-acetone 100 grams, triaryl matte hexafluoro antimonate 180 grams.
2. be heated to 40 ℃, stirred 30 minutes, make it to become the transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.Record its critical exposure E
cBe 12.4 mJ/cm
2
3. the SLA-3500 type Ultra-Violet Laser that utilizes 3D Systems company to produce has solidified the rapid shaping equipment making some test blocks then, are in the 500 milliwatt ultraviolet casees at power, and these test blocks were solidified 90 minutes in the back.Record their warp factor CF (6)=0.01, CF (11)=0.03.
Embodiment 3.
1. in the special 5000 milliliters glass there-necked flask of stirrer and condenser pipe is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-cyclohexyl methyl esters 1000 grams; Bisphenol A type epoxy resin (E-51) 650 grams, tripropylene glycol diacrylate 350 grams, polycaprolactone trihydroxy alcohol (Polyol0301) 200 grams; Trimethylolpropane triacrylate 300 grams; Triethylene glycol divinyl ether 210 grams, styrax dimethyl ether 100 grams, triaryl matte hexafluoro antimonate 190 grams.
2. be heated to 50 ℃, stirred 20 minutes, make it to become the transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.Record its critical exposure E
cBe 12.9 mJ/cm
2
3. the SLA-3500 type Ultra-Violet Laser that utilizes 3D Systems company to produce has solidified the rapid shaping equipment making some test blocks then, are in the 500 milliwatt ultraviolet casees at power, and these test blocks were solidified 90 minutes in the back.Record their warp factor CF (6)=-0.01, CF (11)=0.03.
Embodiment 4.
1. in the special 5000 milliliters glass there-necked flask of stirrer and condenser pipe is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-cyclohexyl methyl esters 1000 grams, 4,5-epoxy hexane-1; 2-dioctyl phthalate 2-glycidyl ester 600 grams, bisphenol-a epoxy acrylate (EA-612) 400 grams, tripropylene glycol diacrylate 300 grams; Polycaprolactone trihydroxy alcohol (Polyol0301) 200 grams; Triethylene glycol divinyl ether 200 grams, 1-hydroxy cyclohexyl phenylketone 100 grams, triaryl matte hexafluoro antimonate 200 grams.
2. be heated to 35 ℃, stirred 60 minutes, make it to become the transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.Record its critical exposure E
cBe 10.7 mJ/cm
2
3. the SLA-3500 type Ultra-Violet Laser that utilizes 3D Systems company to produce has solidified the rapid shaping equipment making some test blocks then, are in the 500 milliwatt ultraviolet casees at power, and these test blocks were solidified 90 minutes in the back.Record their warp factor CF (6)=0.01, CF (11)=0.03.
Embodiment 5.
1. in the special 5000 milliliters glass there-necked flask of stirrer and condenser pipe is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-cyclohexyl methyl esters 1000 grams, 1, two [(3-ethyl-3-oxygen methylene oxetanes) methyl] benzene 400 grams of 4-; Phenol aldehyde type epoxy resin (F-51) 300 grams, bisphenol-a epoxy acrylate (EA-612) 400 grams, tripropylene glycol diacrylate 200 grams; Polycaprolactone dibasic alcohol (Polyol0201)) 200 grams, 1,4-cyclohexyl dimethanol divinyl ether 200 grams; 1-hydroxy cyclohexyl phenylketone 100 grams, triaryl matte hexafluoro antimonate 200 grams.
2. be heated to 65 ℃, stirred 10 minutes, become the transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.Record its critical exposure E
cBe 10.7 mJ/cm
2
3. the SLA-3500 type Ultra-Violet Laser that utilizes 3D Systems company to produce has solidified the rapid shaping equipment making some test blocks then, are in the 500 milliwatt ultraviolet casees at power, and these test blocks were solidified 90 minutes in the back.Record their warp factor CF (6)=-0.01, CF (11)=-0.03.
Embodiment 6.
1. in the special 5000 milliliters glass there-necked flask of stirrer and condenser pipe is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-cyclohexyl methyl esters 1500 grams, phenol aldehyde type epoxy resin (F-51) 400 grams, 1,4-butanediol diglycidyl ether 600 grams, polycaprolactone dibasic alcohol (Polyol0201)) 290 grams, triaryl matte hexafluoro antimonate 210 grams.
2. be heated to 55 ℃, stirred 15 minutes, become the transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.Record its critical exposure E
cBe 14.6 mJ/cm
2
3. the SLA-3500 type Ultra-Violet Laser that utilizes 3D Systems company to produce has solidified the rapid shaping equipment making some test blocks then, are in the 500 milliwatt ultraviolet casees at power, and these test blocks were solidified 90 minutes in the back.Record their warp factor CF (6)=0.00, CF (11)=0.01.
Embodiment 7.
1. in the special 5000 milliliters glass there-necked flask of stirrer and condenser pipe is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-cyclohexyl methyl esters 1000 grams, bisphenol A type epoxy resin (E-51) 1000 grams, 1,4-cyclohexyl dimethanol divinyl ether 500 grams, polycaprolactone trihydroxy alcohol (Polyol0301)) 270 grams, triaryl matte hexafluoro antimonate 230 grams.
2. be heated to 45 ℃, stirred 60 minutes, become the transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.Record its critical exposure E
cBe 11.2mJ/cm
2
3. the SLA-3500 type Ultra-Violet Laser that utilizes 3D Systems company to produce has solidified the rapid shaping equipment making some test blocks then, are in the 500 milliwatt ultraviolet casees at power, and these test blocks were solidified 90 minutes in the back.Record their warp factor CF (6)=0.01, CF (11)=0.02.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from spirit of the present invention with away from the change of being made down, modification, substitute, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (16)
1. the rapid-result type photosensitive resin of a Ultra-Violet Laser quick solidifying is characterized in that being made up of following raw material by the quality proportioning:
Epoxy resin 5～80%
Oxetane compound 0～65%
Cationic initiating agent 1～12%
Hydroxyl organic compound 1～40%
The unsaturated oligomer 0～55% that contains carbon-to-carbon double bond
The unsaturated monomer 0～35% that contains carbon-to-carbon double bond
Low-molecular-weight glycidol ether or title epoxide diluent 0～20%
Free radical type Photoepolymerizationinitiater initiater 0～10%.
2. the rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying according to claim 1, the said epoxy resin of its characteristic are phenol aldehyde type epoxy resin, bisphenol A type epoxy resin, cycloaliphatic epoxy resin or claim the one or more kinds of potpourris in the alicyclic epoxide compound.
3. the rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying according to claim 1 and 2, the said epoxy resin of its characteristic is 3,4-epoxycyclohexyl formic acid-3
', 4
'-epoxycyclohexyl methyl esters.
4. the rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying according to claim 1, the said oxetane compound of its characteristic is the organism that contains two oxetane groups, three oxetane groups or a plurality of oxetane groups.
5. the rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying according to claim 1, the described cationic initiating agent of its characteristic is salt compounded of iodine or sulfonium salt.
6. according to claim 1 or the rapid-result type photosensitive resin of 5 described Ultra-Violet Laser quick solidifyings, the described cationic initiating agent of its characteristic is triaryl matte hexafluorophosphate, triaryl matte hexafluoro arsenate or triaryl matte hexafluoro antimonate.
7. the rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying according to claim 1, the described hydroxyl organic compound of its characteristic is the organism of the organism of the organism that contains an oh group, two oh groups, three oh groups or the organism of a plurality of oh groups.
8. according to claim 1 or the rapid-result type photosensitive resin of 7 described Ultra-Violet Laser quick solidifyings, the described hydroxyl organic compound of its characteristic is polycaprolactone dibasic alcohol or polycaprolactone trihydroxy alcohol.
9. the rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying according to claim 1, the described unsaturated oligomer that contains carbon-to-carbon double bond of its characteristic is epoxy acrylate, urethane acrylate, polyester acrylate, amino acrylates, polyether acrylate, pure acrylic acid ester or organosilicon, Organic fluoride acrylic ester.
10. according to claim 1 or the rapid-result type photosensitive resin of 9 described Ultra-Violet Laser quick solidifyings, the described unsaturated oligomer that contains carbon-to-carbon double bond of its characteristic is a bisphenol-a epoxy acrylate.
11. the rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying according to claim 1, the described unsaturated monomer that contains carbon-to-carbon double bond of its characteristic is acrylate monomer or vinyl ether monomers.
12. according to claim 1 or the rapid-result type photosensitive resin of 11 described Ultra-Violet Laser quick solidifyings; Acrylate monomer or vinyl ether monomers that the described unsaturated monomer that contains carbon-to-carbon double bond of its characteristic is two above carbon-to-carbon double bonds, perhaps their mix monomer.
13. the rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying according to claim 1, the described low-molecular-weight glycidol ether of its characteristic is the low-molecular-weight glycidol ether that contains two or more epoxide groups.
14. according to claim 1 or the rapid-result type photosensitive resin of 13 described Ultra-Violet Laser quick solidifyings, the described low-molecular-weight glycidol ether of its characteristic is ethylene glycol diglycidylether, tripropyleneglycol diglycidyl ether or 1, the 4-butanediol diglycidyl ether.
15. the rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying according to claim 1, the described free radical type Photoepolymerizationinitiater initiater of its characteristic is for can cause the free radical type initiating agent that all unsaturated monomers that contain carbon-to-carbon double bond carry out polymerization.
16. according to claim 1 or the rapid-result type photosensitive resin of 15 described Ultra-Violet Laser quick solidifyings, the described free radical type Photoepolymerizationinitiater initiater of its characteristic is benzophenone, styrax dimethyl ether, chlorinated diphenyl ketone, 4-benzoyl-4
'-dimethyl diphenyl sulfide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy cyclohexyl phenylketone or 2, the one or more kinds of potpourris in the 4-diethyl thioxanthone.
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| CN109485829A (en) * | 2018-09-25 | 2019-03-19 | 南昌大学 | A kind of high-precision and high flexibility stereolithography 3D printing photosensitive resin and preparation method |
| CN109485829B (en) * | 2018-09-25 | 2021-03-26 | 南昌大学 | High-precision and high-flexibility stereolithography 3D printing photosensitive resin and preparation method thereof |
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