CN102436145B - Stereo lithography rapid prototyping photosensitive resin and preparation method thereof - Google Patents
Stereo lithography rapid prototyping photosensitive resin and preparation method thereof Download PDFInfo
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- CN102436145B CN102436145B CN 201110255401 CN201110255401A CN102436145B CN 102436145 B CN102436145 B CN 102436145B CN 201110255401 CN201110255401 CN 201110255401 CN 201110255401 A CN201110255401 A CN 201110255401A CN 102436145 B CN102436145 B CN 102436145B
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Abstract
The invention relates to a stereo lithography rapid prototyping photosensitive resin which is characterized by comprising the following raw materials according to the mass ratio: 5-30% of ethylene glycol diglycidyl ether diacrylate, 5-75% of epoxy resin, 5-55% of oxacyclobutane compound, 1-12% of cationic initiator, 5-50% of acrylic ester prepolymer and 1-10% of radical photopolymerization initiator. A preparation method of the stereo lithography rapid prototyping photosensitive resin comprises the steps of: mixing the raw material components according to the mass ratio; and then, heating and stirring, namely, stirring for 5-120 minutes at the temperature of 20-80 DEG C, and leading the obtained mixture to become transparent faint yellow uniform liquid. The photosensitive resin is low in irritation and less in volatile matter, and has good light sensitivity, wherein the critical exposure Ec is less than 16.5mJ/ cm<2>; a molded part is high in accuracy and has the warpage factors CF (6) within the range of 0.01 to -0.01 and CF (11) within the range of 0.03 to -0.03; and parts with any complicated shapes and high accuracy can be directly manufactured, and the manufacturing cost is very low.
Description
Technical field
The invention belongs to rapid shaping and make the field, relate to rapid shaping photosensitive resin and preparation.
Background technology
Since U.S. 3D Systems company in 1988 releases stereolithography rapid shaping machine the earliest, this forming machine with the complexity that can automatically produce various job operations and be difficult to make the three-dimensional shape object, have epoch-making meaning in processing technique field.It is take liquid photosensitive resin as raw material, under the control of computing machine, Ultra-Violet Laser is pressed each layering cross-section data liquid towards photosensitive resin surface point by point scanning of part, makes the thin resin layer that is scanned the zone produce photopolymerization reaction and solidify, and forms a thin layer of part; After one deck curing was complete, worktable descended, and applied the new liquid resin of one deck at the resin surface that originally was cured again and solidified in order to carry out lower one deck scanning; New one deck that solidifies is bonded in again on front one deck securely; So repeat, until the making of whole part is complete.In the stereolithography quick shaping process, photosensitive resin is its basis, and its composition and ultraviolet-curing paint, printing ink form somewhat identical, namely are comprised of light trigger, prepolymer, thinning agent and a small amount of adjuvant.But the stereolithography quick shaping process has specific (special) requirements to its photosensitive resin, and it requires photosensitive resin to have following characteristics: (1) viscosity is low, and Low viscosity resin is conducive to the very fast levelling of resin energy in moulding; (2) pungency is little few with volatile matter, is conducive to operator's health and does not cause environmental pollution; (3) cure shrinkage is little, and light-cured resin can produce internal stress and shrink in being converted into solid-state process by liquid state, and this contraction can cause the distortion of original paper in manufacturing process, warpage, cracking etc., and the precision of forming part is reduced; (4) swelling is little, and the swelling of hygrometric state profiled member in the resin of liquid state can cause accessory size bigger than normal; (5) susceptibility to light is high, and namely the scope of institute's absorbing wavelength is narrow, to improve the making precision of part; (6) good with the light source matching, to take full advantage of luminous energy, improve and solidify yield; (7) resin bonding is strong, does not produce splitting to guarantee rear solidification process; (8) solidification rate is fast, to enhance productivity; (9) bin stability is good, and general storage life is Ying Yinian at least; (10) cost is low, is beneficial to commercialization.Because the required photosensitive resin of stereolithography rapid shaping needs to satisfy simultaneously above these characteristics, cause its photosensitive resin research and development to have certain difficulty.
Now, foreign applications is mainly that free radical-cation type mixes type photosensitive resin in the photosensitive resin of stereolithography rapid shaping, the characteristics of this photosensitive resin be prepolymer and thinning agent take epoxy resin as main, acrylate is auxiliary.This photosensitive resin has been concentrated the advantage that the acrylate curing rate is fast and the epoxy resin cure contraction is little, and making it photosensitive resin, both to have had photosensitivity good, has again high characteristics of profiled member precision.For example, the photosensitive resin of the photosensitive resin of U.S. DSM Somos company and Huntsman company just belongs to free radical-cation type and mixes type photosensitive resin.Now, this two company sells to China up to 1500 yuans take selling price as per kilogram, and is monopolizing the market of China's stereolithography rapid shaping photosensitive resin.
At home, in recent ten years, there are many universities and scientific research institute, place to carry out the research of stereolithography rapid shaping photosensitive resin, obtained some achievements.But also not deeply, at present, domestic having two parts of patents of invention aspect the research of stereolithography rapid shaping photosensitive resin in research.The Guangzhou Inst. of Machinery Science Haitao Liu, Zhong Hanrong and Xue Jidong have proposed " a kind of stereolithography rapid prototyping photosensitive resin and its preparation method and application ", and the number of applying for a patent is 200910040526.1.The king of Zhejiang Polytechnical University sea moral, Malaysian is outstanding, and Sun Xing equality has proposed " a kind of UV curing photosensitive resin for rapid moulding injection mold ", and the number of applying for a patent is 200910095846.7.In these two parts of applications, when they prepare photosensitive resin, thinning agent used is trimethylolpropane triacrylate, tripropylene glycol diacrylate and 1,6-hexanediyl ester etc., and these thinning agent volatility are large and pungency is large, and working environment is had certain pollution.Therefore, these two parts of patents all seem a bit not enough.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art part, the ethylene glycol diglycidylether diacrylate little volatility, that pungency is little and viscosity is low prepares stereolithography rapid shaping photosensitive resin as thinning agent.
The present invention is achieved through the following technical solutions.
Stereolithography rapid shaping photosensitive resin of the present invention is comprised of following raw material by the quality proportioning:
5～30% ethylene glycol diglycidylether diacrylates
5～75% epoxy resin
5～55% oxetane compounds
1～12% cationic initiating agent
5～50% acrylic ester prepolymers
1～10% free radical type Photoepolymerizationinitiater initiater.
Epoxy resin of the present invention is the one or more kinds of potpourris in bisphenol A type epoxy resin, phenol aldehyde type epoxy resin, cycloaliphatic epoxy resin or title alicyclic epoxide compound.Preferred cycloaliphatic epoxy resin, for example, 3,4-epoxycyclohexyl formic acid-3
', 4
'-epoxycyclohexyl methyl esters.
Oxetane compound of the present invention is 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 contain two oxetane groups, the serial organism of three oxetane groups and a plurality of oxetane groups.
Cationic initiating agent of the present invention is salt compounded of iodine or sulfonium salt, wherein mainly refers to diaryl iodine hexafluorophosphate, diaryl iodine hexafluoro arsenate, diaryl iodine hexafluoro antimonate and triaryl matte hexafluorophosphate, triaryl matte hexafluoro arsenate, triaryl matte hexafluoro antimonate etc.Preferred triaryl matte hexafluorophosphate, triaryl matte hexafluoro arsenate and triaryl matte hexafluoro antimonate.
Acrylic ester prepolymer of the present invention is epoxy acrylate, urethane acrylate, polyester acrylate, amino acrylates, polyether acrylate, pure acrylate and organosilicon or Organic fluoride acrylate etc.Preferred epoxy acrylate mainly refers to bisphenol-a epoxy acrylate.
Free radical type Photoepolymerizationinitiater initiater of the present invention is for can cause the free radical type initiating agent that all unsaturated monomers that contain carbon-to-carbon double bond carry out polymerization.Preferred benzophenone, dimethoxybenzoin, chlorinated diphenyl ketone, 4-benzoyl-4
'One or more kinds of potpourris in-dimethyl diphenyl sulfide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy cyclohexyl phenylketone or 2,4-diethyl thioxanthone.
The present invention also provides the preparation method of stereolithography rapid shaping photosensitive resin, is that described material component is mixed by described quality proportioning; Then, heating, stirring namely 20～80 ℃ of temperature, were stirred 5～120 minutes, made it to become transparent faint yellow uniform liquid.
The synthetic method of ethylene glycol diglycidylether diacrylate of the present invention see " Huang Biwu etc. ethylene glycol diglycidylether diacrylate synthetic and use [J]. Central China University of Science and Technology's journal (natural science edition); 2004,32 (11): 27-29 ".
Ultimate principle of the present invention is as follows.
Now, on the home market, the popular acrylate monomer as thinning agent is trimethylolpropane triacrylate (TMPTA), tripropylene glycol diacrylate (TPGDA) and 1,6-hexanediyl ester (HDDA) etc., because they have larger smell and to the larger pungency of skin and larger volatility, and will progressively be eliminated by market.Therefore, develop novel low smell and skin low irritant, hypotoxic acrylate monomer are seemed extremely important.In view of ethylene glycol diglycidylether diacrylate has the advantages that pungency is little, volatility is little and viscosity is low, can consider to select it to prepare stereolithography rapid shaping photosensitive resin as the thinning agent of photosensitive resin.
has less shrinkability when solidifying for the stereolithography rapid shaping photosensitive resin that makes preparation, product has higher precision, the present invention suitably adopts epoxy resin for the prepolymer of photosensitive resin more, oxetanes or their potpourri, suitably lack spent glycol diglycidyl ether diacrylate and acrylic ester prepolymer, because epoxy resin, the polymerization of oxetanes is ring-opening polymerization, shrink little, and the polymerization of ethylene glycol diglycidylether diacrylate and acrylic ester prepolymer is the polymerization that the carbon-to-carbon double bond fracture becomes singly-bound, shrink greatly.Yet, for the photosensitive resin that makes preparation has photosensitivity preferably, need to adopt as much as possible ethylene glycol diglycidylether diacrylate and acrylic ester prepolymer as raw material, use less epoxy resin, oxetanes as raw material because ethylene glycol diglycidylether diacrylate and acrylic ester prepolymer under UV-irradiation its solidification rate faster than the solidification rate of epoxy resin and oxetanes.In order to make photosensitive resin can keep high precision when the product and to take into account the photosensitivity of photosensitive resin, should adopt epoxy resin and oxetanes to adopt again ethylene glycol diglycidylether diacrylate and acrylic ester prepolymer during the preparation photosensitive resin, good this balance of GPRS.In order to prepare stereolithography rapid shaping photosensitive resin, the present invention also selects ultraviolet initiator.The cationic initiating agent that initiating agent is preferably selected to comprise the free radical type initiating agent of initiating methacrylates polymerization and caused epoxy resin and oxetanes polymerization.To notice considering that initiating agent has response preferably to the specific wavelength ultraviolet light that ultraviolet laser sends when selecting initiating agent, namely the 355nm ultraviolet light be 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, and because being adds ethylene glycol diglycidylether diacrylate as thinning agent, so the photosensitive resin pungency is little and volatile matter is few.Secondly, the photosensitivity of photosensitive resin is good, its critical exposure E
cLess than 16.5mJ/cm
2Secondly, the precision of forming part is high, and the warp factor CF of forming part (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 of per kilogram, far below the selling price (approximately 1500 yuans of per kilograms) of the photosensitive resin of DSM Somos company and Huntsman company.
Embodiment
Below in conjunction with embodiment, the present invention is done further describing in detail, but implementation of the present invention is not limited to this.
Embodiment 1.
1. in the glass there-necked flask of special 5000 milliliters of stirrer and condenser pipe is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-epoxycyclohexyl methyl esters 900 grams, bisphenol A type epoxy resin (E-51) 600 grams, 3,3-[oxygen base dimethylene]-two [3-ethyl] oxetanes 400 grams, bisphenol-a epoxy acrylate (EA-612) 680 grams, ethylene glycol diglycidylether diacrylate 150 grams, dimethoxybenzoin 100 grams, triaryl matte hexafluoro antimonate 170 grams.
2. be heated to 50 ℃, stirred 30 minutes, make it to become transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.Record its critical exposure E
cBe 16.2 mJ/cm
2, method of testing be adopt " Zhao Yi. the experimental study of photosensitive resin characteristic [J] in laser fast forming. polymer material science and engineering, 2004,20(1): 184-186 " method reported.
3. the SLA-3500 type ultraviolet laser solidification rapid forming equipment that utilizes 3D Systems company to produce has been made some test blocks, then, is in 500 milliwatt ultraviolet casees at power, these test blocks of rear curing 90 minutes.Record their warp factor CF (6)=0.01, CF (11)=0.03.For ultraviolet laser solidification rapid shaping photosensitive resin make the precision evaluation standard of part existing popular be the warp factor evaluation method, what its method adopted is the method for formulating in the international Quick-forming meeting of Second Committee of holding in 1991.
Embodiment 2.
1. in the glass there-necked flask of special 5000 milliliters of stirrer and condenser pipe is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-epoxycyclohexyl methyl esters 1000 grams, bisphenol A type epoxy resin (E-51) 500 grams, 3,3-[oxygen base dimethylene]-two [3-ethyl] oxetanes 400 grams, bisphenol-a epoxy acrylate (EA-612) 530 grams, ethylene glycol diglycidylether diacrylate 300 grams, 2-hydroxy-2-methyl-1-phenyl-1-acetone 100 grams, triaryl matte hexafluoro antimonate 170 grams.
2. be heated to 40 ℃, stirred 30 minutes, make it to become transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.Record its critical exposure E
cBe 15.4 mJ/cm
2
3. the SLA-3500 type ultraviolet laser solidification rapid forming equipment that utilizes 3D Systems company to produce has been made some test blocks, then, is in 500 milliwatt ultraviolet casees at power, these test blocks of rear curing 90 minutes.Record their warp factor CF (6)=0.01, CF (11)=-0.02.
Embodiment 3.
1. in the glass there-necked flask of special 5000 milliliters of stirrer and condenser pipe is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-epoxycyclohexyl methyl esters 1000 grams, bisphenol A type epoxy resin (E-51) 400 grams, 3,3-[oxygen base dimethylene]-two [3-ethyl] oxetanes 500 grams, bisphenol-a epoxy acrylate (EA-612) 430 grams, ethylene glycol diglycidylether diacrylate 400 grams, dimethoxybenzoin 100 grams, triaryl matte hexafluoro antimonate 170 grams.
2. be heated to 50 ℃, stirred 20 minutes, make it to become 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 ultraviolet laser solidification rapid forming equipment that utilizes 3D Systems company to produce has been made some test blocks, then, is in 500 milliwatt ultraviolet casees at power, these test blocks of rear curing 90 minutes.Record their warp factor CF (6)=-0.01, CF (11)=0.02.
Embodiment 4.
1. in the glass there-necked flask of special 5000 milliliters of stirrer and condenser pipe is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-epoxycyclohexyl methyl esters 1000 grams, bisphenol A type epoxy resin (E-51) 400 grams, 3,3-[oxygen base dimethylene]-two [3-ethyl] oxetanes 400 grams, bisphenol-a epoxy acrylate (EA-612) 480 grams, ethylene glycol diglycidylether diacrylate 450 grams, 1-hydroxy cyclohexyl phenylketone 100 grams, triaryl matte hexafluoro antimonate 170 grams.
2. be heated to 35 ℃, stirred 60 minutes, make it to become transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.Record its critical exposure E
cBe 13.6 mJ/cm
2
3. the SLA-3500 type ultraviolet laser solidification rapid forming equipment that utilizes 3D Systems company to produce has been made some test blocks, then, is in 500 milliwatt ultraviolet casees at power, these test blocks of rear curing 90 minutes.Record their warp factor CF (6)=0.01, CF (11)=-0.01.
Embodiment 5.
1. in the glass there-necked flask of special 5000 milliliters of stirrer and condenser pipe is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-epoxycyclohexyl methyl esters 1000 grams, bisphenol A type epoxy resin (E-51) 450 grams, 3,3-[oxygen base dimethylene]-two [3-ethyl] oxetanes 350 grams, bisphenol-a epoxy acrylate (EA-612) 430 grams, ethylene glycol diglycidylether diacrylate 500 grams, 1-hydroxy cyclohexyl phenylketone 95 grams, triaryl matte hexafluoro antimonate 175 grams.
2. be heated to 65 ℃, stirred 10 minutes, become 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 ultraviolet laser solidification rapid forming equipment that utilizes 3D Systems company to produce has been made some test blocks, then, is in 500 milliwatt ultraviolet casees at power, these test blocks of rear curing 90 minutes.Record their warp factor CF (6)=-0.01, CF (11)=-0.02.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from Spirit Essence of the present invention with away from the lower change of making, modification, substitute, combination, simplify; all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (12)
1. stereolithography rapid shaping photosensitive resin is characterized in that being comprised of following raw material by the quality proportioning:
5～30% ethylene glycol diglycidylether diacrylates
5～75% epoxy resin
5～55% oxetane compounds
1～12% cationic initiating agent
5～50% acrylic ester prepolymers
1～10% free radical type Photoepolymerizationinitiater initiater.
2. stereolithography rapid shaping photosensitive resin according to claim 1, is characterized in that described epoxy resin is the one or more kinds of potpourris in bisphenol A type epoxy resin, phenol aldehyde type epoxy resin, cycloaliphatic epoxy resin or title alicyclic epoxide compound.
3. stereolithography rapid shaping photosensitive resin according to claim 2, is characterized in that described epoxy resin is 3,4-epoxycyclohexyl formic acid-3
', 4
'-epoxycyclohexyl methyl esters.
4. stereolithography rapid shaping photosensitive resin according to claim 1, is characterized in that described oxetane compound is the organism that contains oxetane groups.
5. stereolithography rapid shaping photosensitive resin according to claim 4, is characterized in that described oxetane compound is the organism that contains two oxetane groups, three oxetane groups or a plurality of oxetane groups.
6. stereolithography rapid shaping photosensitive resin according to claim 1, is characterized in that described cationic initiating agent is salt compounded of iodine or sulfonium salt.
7. stereolithography rapid shaping photosensitive resin according to claim 6, is characterized in that described cationic initiating agent is diaryl iodine hexafluorophosphate, diaryl iodine hexafluoro arsenate, diaryl iodine hexafluoro antimonate, triaryl matte hexafluorophosphate, triaryl matte hexafluoro arsenate or triaryl matte hexafluoro antimonate.
8. stereolithography rapid shaping photosensitive resin according to claim 1, is characterized in that described acrylic ester prepolymer is epoxy acrylic ester prepolymer, polyurethane acrylate prepolymer, polyester acrylic ester prepolymer, amino acrylates prepolymer, polyether acrylate prepolymer, pure acrylate prepolymer, acid-organosilicon crylic acid prepolymer or Organic fluoride acrylic ester prepolymer.
9. stereolithography rapid shaping photosensitive resin according to claim 8, is characterized in that described acrylic ester prepolymer is the bisphenol-a epoxy acrylate prepolymer.
10. stereolithography rapid shaping photosensitive resin according to claim 1, is characterized in that described free radical type Photoepolymerizationinitiater initiater is for can cause the free radical type initiating agent that all unsaturated monomers that contain carbon-to-carbon double bond carry out polymerization.
11. stereolithography rapid shaping photosensitive resin according to claim 10 is characterized in that described free radical type Photoepolymerizationinitiater initiater is benzophenone, dimethoxybenzoin, chlorinated diphenyl ketone, 4-benzoyl-4
'One or more kinds of potpourris in-dimethyl diphenyl sulfide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy cyclohexyl phenylketone or 2,4-diethyl thioxanthone.
12. the preparation method of the described stereolithography rapid shaping of a claim 1-11 any one photosensitive resin is characterized in that described material component is mixed by described quality proportioning; Then, heating, stirring namely 20～80 ℃ of temperature, were stirred 5～120 minutes, made it to become transparent faint yellow uniform liquid.
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| CN102981362A (en) * | 2012-11-14 | 2013-03-20 | 南昌大学 | Method using 4 and 5-cyclohexene oxide-1 and 2-dioctyl phthalate glycidyl ester as prepolymer to prepare three-dimensional lithography fast forming photosensitive resin and application |
| CN104250422A (en) * | 2013-06-26 | 2014-12-31 | 合肥杰事杰新材料股份有限公司 | Photosensitive resin used in 3D printing, and its preparation method |
| CN105404095A (en) * | 2015-12-23 | 2016-03-16 | 河南工程学院 | Washable ultraviolet laser curing and rapid prototyping photosensitive resin and preparation method thereof |
| CN105399908B (en) * | 2015-12-23 | 2018-02-02 | 河南工程学院 | A kind of ultraviolet laser solidification rapid shaping photosensitive resin and preparation method thereof |
| CN106221177A (en) * | 2016-07-26 | 2016-12-14 | 苏州秉创科技有限公司 | A kind of injecting type 3D prints photo-curing material |
| CN107698722A (en) * | 2016-08-08 | 2018-02-16 | 惠展电子材料（上海）有限公司 | Photosensitive resin of ultraviolet laser solidification and preparation method thereof |
| CN108314911A (en) * | 2017-01-17 | 2018-07-24 | 常州格林感光新材料有限公司 | A kind of UVLED curable wood coatings |
| CN107357136A (en) * | 2017-08-23 | 2017-11-17 | 广西众昌树脂有限公司 | Photosensitive liquid resin |
| CN109467651B (en) * | 2018-11-07 | 2021-01-15 | 华东理工大学华昌聚合物有限公司 | Light-cured epoxy vinyl ester resin and synthetic method thereof |
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| CN101631817A (en) * | 2007-03-14 | 2010-01-20 | 亨斯迈先进材料（瑞士）有限公司 | Curable composition |
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