CN102432840A - Stereolithography rapid protoyping photosensitive resin prepared by using polypropylene glycol diglycidyl ether diacrylate as prepolymer, and preparation method for stereolithography rapid protoyping photosensitive resin - Google Patents
Stereolithography rapid protoyping photosensitive resin prepared by using polypropylene glycol diglycidyl ether diacrylate as prepolymer, and preparation method for stereolithography rapid protoyping photosensitive resin Download PDFInfo
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- CN102432840A CN102432840A CN2011103275939A CN201110327593A CN102432840A CN 102432840 A CN102432840 A CN 102432840A CN 2011103275939 A CN2011103275939 A CN 2011103275939A CN 201110327593 A CN201110327593 A CN 201110327593A CN 102432840 A CN102432840 A CN 102432840A
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Abstract
The invention discloses a stereolithography rapid protoyping photosensitive resin prepared by using polypropylene glycol diglycidyl ether diacrylate as prepolymer, and a preparation method for the stereolithography rapid protoyping photosensitive resin. The resin is characterized by being prepared from the following raw materials in percentage by mass: 10 to 70 percent of polypropylene glycol diglycidyl ether diacrylate, 5 to 75 percent of epoxy resin, 5 to 55 percent of oxacyclobutane compound, 1 to 12 percent of cationic initiator, and 1 to 10 percent of free radical photopolymerization initiator. The method comprises the following steps of: mixing the raw materials in the mass ratio, and stirring at the temperature of between 20 and 80 DEG C for 5 to 120 minutes to ensure that a mixture becomes transparent faint yellow uniform liquid. The prepared photosensitive resin is low in irritation and volatile matter content, and is easy and convenient to prepare, and is high in photosensitiveness; and the critical exposure capacity Ec of the resin is less than 16.0mJ/cm<2>; formed parts are high in precision, and the camber factor CF(6) of the formed parts is +/-0.01, and CF (11) is +/-0.03. Parts with any complex shape and high precision can be directly prepared from the resin and the preparation cost of the resin is much lower than that of the photosensitive resins of the same kind.
Description
Technical field
The invention belongs to rapid shaping and make the field, relate to the polypropylene glycol diglycidyl ether diacrylate in preparation stereolithography rapid shaping photosensitive resin as prepolymer and application.
Background technology
The appearance of rapid shaping makes manufacturing complicated shape or mould become simple and quick.Quick shaping process commonly used is that Ultra-Violet Laser curing rapid shaping (is commonly called as: the stereolithography rapid shaping); It is to utilize Ultra-Violet Laser shape point by point scanning by two-dimensional section on the photosensitive resin liquid level; Make resin solidification; Resin after the curing just forms an X-Y scheme, so successively scans, solidifies, and finally can obtain complete 3D solid.In the stereolithography rapid shaping, used photosensitive resin is on the basis of traditional ultraviolet-curing paint, to grow up.Early stage i.e. 1988-nineteen ninety-five, commercial stereolithography rapid shaping photosensitive resin all was with the free radical type photosensitive resin of propenoate as prepolymer, 2100,3100 and 3110 types of researching and developing like 5081 and 5149 types and the Du Pont company of Ciba-Geigy company research and development etc.Advantages such as it is cheap that though this type free fundamental mode photosensitive resin has, and solidification rate is fast, because cure shrinkage is serious, the product warpage is obvious, and precision is difficult to meet the demands, and finally still is eliminated.
Now, the photosensitive resin that is applied to the stereolithography rapid shaping abroad mainly is that free radical-cation type mixes type photosensitive resin, and the characteristics of this photosensitive resin are that prepolymer and thinner are main with epoxy resin, and propenoate is auxilliary.This photosensitive resin concentrated the propenoate curing speed fast with the little advantage of epoxy resin cure contraction, making it photosensitive resin, both to have had photosensitivity good, has the high characteristics of profiled member precision again.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 is that per kilogram is sold to China up to 1500 yuans with the selling price, 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 have two parts in invention disclosed patent aspect the research of stereolithography rapid shaping photosensitive resin in research.Guangzhou Inst. of Machinery Science Haitao Liu, Zhong Hanrong and Xue Jidong have proposed " a kind of stereolithography rapid prototyping photosensitive resin ", and number of patent application is 200910040526.1.The king of Zhejiang Polytechnical University sea moral, Malaysian outstanding person, Sun Xing equality have proposed " a kind of UV curing photosensitive resin for rapid moulding injection mold ", and number of patent application is 200910095846.7.In these two parts of patents; Used esters of acrylic acid prepolymer was bisphenol-a epoxy acrylate, phenolic epoxy propenoate and pentaerythritol triacrylate etc. when they prepared photosensitive resin; The shortcoming of these prepolymers is that cured article is more crisp, and the prepolymer viscosity is bigger, causes needs to add the less thinner Viscoat 295 of viscosity; Tripropylene glycol diacrylate and 1; 6-hexanediyl ester or the like is regulated the photosensitive resin viscosity, and these thinner volatility are big and pungency is big, and Working environment is had certain pollution.Therefore, these two parts of applications all seem a bit not enough.
Summary of the invention
The objective of the invention is to overcome the weak point of prior art; The polypropylene glycol diglycidyl ether diacrylate little volatility, that pungency is little and viscosity is moderate prepares stereolithography rapid shaping photosensitive resin as prepolymer; And need not to add prepolymers such as bisphenol-a epoxy acrylate, phenolic epoxy propenoate and pentaerythritol triacrylate; Simultaneously can avoid adding the thinner Viscoat 295; Tripropylene glycol diacrylate and 1,6 hexanediol diacrylate wait and prepare stereolithography rapid shaping photosensitive resin.
The present invention realizes through following technical scheme.
Polypropylene glycol diglycidyl ether diacrylate of the present invention does not have commodity purchasing on the market temporarily; The used polypropylene glycol diglycidyl ether diacrylate of the present invention is synthetic for this laboratory; Its compound method see " HUANG Biwu; et al. Synthesis of a novel UV-curable prepolymer polypropyleneglycol diglycidyl ether diacrylate [J]. Journal of Wuhan University of Technology (Material Science Edition) 2008,23 (4): 495-498 ".
Stereolithography rapid shaping photosensitive resin of the present invention is made up of following raw material by the quality proportioning:
10~70% polypropylene glycol diglycidyl ether diacrylate
5~75% epoxy resin
5~55% oxetane compounds
1~12% cationic initiator
1~10% free radical type Photoepolymerizationinitiater initiater.
Epoxy resin according to the invention is bisphenol A type epoxy resin, phenol aldehyde type epoxy resin, cycloaliphatic epoxy resin or claims one or more the mixture in the 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 the organism that contains oxetane groups, and it comprises the organism that contains an oxetane groups, two oxetane groups, three oxetane groups and a plurality of oxetane groups.The organism that preferably contains two oxetane groups, three oxetane groups or a plurality of oxetane groups.
Cationic initiator of the present invention is salt compounded of iodine or 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.Preferred triaryl matte hexafluorophosphate, triaryl matte hexafluoro arsenate or triaryl matte hexafluoro antimonate.
Free radical type Photoepolymerizationinitiater initiater of the present invention carries out polymeric free radical type initiator for causing all unsaturated monomers that contain carbon-to-carbon double bond.Preferred UVNUL MS-40, st-yrax dme, diphenyl antimony chloride ketone, 4-benzoyl--4
'-dimethyl diphenyl sulfide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy cyclohexyl phenylketone or 2, one or more mixtures in the 4-diethyl thioxanthone.
The present invention also provides the preparation method of stereolithography rapid shaping photosensitive resin, is that the above-mentioned raw materials component is mixed by the quality proportioning; Then, under 20~80 ℃ of temperature, stirred 5~120 minutes, make it to become the transparent faint yellow uniform liquid.
Ultimate principle of the present invention is following.
Now; Popular is bisphenol-a epoxy acrylate, phenolic epoxy propenoate and pentaerythritol triacrylate etc. as stereolithography rapid shaping photosensitive resin esters of acrylic acid prepolymer on the domestic and international market; These prepolymers are because viscosity is bigger, and cured article fragility is big, usually need add acrylate monomer; As: the performance that Viscoat 295, tripropylene glycol diacrylate and 1,6 hexanediol diacrylate etc. are regulated viscosity and cured article as thinner.Therefore; Develop low smell of viscosity Shi Zhong ﹑ and the good esters of acrylic acid prepolymer of cured article snappiness and seem extremely important; And the polypropylene glycol diglycidyl ether diacrylate has above-mentioned characteristics, can consider to select it to prepare stereolithography rapid shaping photosensitive resin as the esters of acrylic acid prepolymer 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 for suitably epoxy resin, trimethylene oxide or their mixtures of adopting of prepolymer of photosensitive resin more; Suitably use the polypropylene glycol diglycidyl ether diacrylate prepolymer less,, shrink little because the polymerization of epoxy resin, trimethylene oxide is ring-opening polymerization; And polypropylene glycol diglycidyl ether diacrylate polyisocyanate polyaddition is the single bonded polymerization of carbon-to-carbon double bond fracture becoming, and shrinks greatly.Yet; For the photosensitive resin that makes preparation has better photosensitivity; Need adopt the polypropylene glycol diglycidyl ether diacrylate prepolymer as raw material as much as possible; Use epoxy resin, trimethylene oxide as raw material less because the polypropylene glycol diglycidyl ether diacrylate prepolymer under UV-irradiation its solidification rate faster than the solidification rate of epoxy resin and trimethylene oxide.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 and trimethylene oxide to adopt the polypropylene glycol diglycidyl ether diacrylate prepolymer again 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.Initiator is preferably selected to comprise initiating methacrylates polymeric free radical type initiator and is caused epoxy resin and the cationic initiator of trimethylene oxide polymeric.When selecting initiator, to notice considering that initiator has responsiveness preferably to the specific wavelength UV-light that ultraviolet laser sent, promptly the 355nm UV-light had responsiveness 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; Owing to be to add the polypropylene glycol diglycidyl ether diacrylate as the esters of acrylic acid prepolymer; So need not to add again prepolymer and propenoate thinners such as bisphenol-a epoxy acrylate, phenolic epoxy propenoate and pentaerythritol triacrylate; Make that like this photosensitive resin pungency of preparation is little few with volatile matter, simultaneously, make the step of preparation photosensitive resin become more easy.Secondly, good with the polypropylene glycol diglycidyl ether diacrylate as the photosensitivity of the photosensitive resin of esters of acrylic acid prepolymer preparation, its critical exposure E
cLess than 16.0mJ/cm
2Again secondly, 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 260 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 whisking appliance and prolong is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-epoxycyclohexyl methyl esters 1000 grams, 3,3-[oxygen base dimethylene]-two [3-ethyl] trimethylene oxide 500 grams; Bisphenol A type epoxy resin (E-51) 410 grams; Polypropylene glycol diglycidyl ether diacrylate 820 grams, st-yrax dme 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 15.1mJ/cm
2, testing method 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, these test blocks of after fixing 90 minutes.Record their warp factor CF (6)=0.01, CF (11)=0.02.The part of the existing popular of precision evaluation standard make to(for) the rapid-result type photosensitive resin of Ultra-Violet Laser quick solidifying is the warp factor evaluation method, and 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 whisking appliance and prolong 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] trimethylene oxide 400 grams, polypropylene glycol diglycidyl ether diacrylate 800 grams; 2-hydroxy-2-methyl-1-phenyl-1-acetone 110 grams, triaryl matte hexafluoro antimonate 190 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 14.9 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, these test blocks of after fixing 90 minutes.Record their warp factor CF (6)=-0.01, CF (11)=-0.02.
Embodiment 3.
1. in the special 5000 milliliters glass there-necked flask of whisking appliance and prolong is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-epoxycyclohexyl methyl esters 500 grams, bisphenol A type epoxy resin (E-51) 900 grams, 3; 3-[oxygen base dimethylene]-two [3-ethyl] trimethylene oxide 400 grams; Polypropylene glycol diglycidyl ether diacrylate 900 grams, st-yrax dme 100 grams, triaryl matte hexafluoro antimonate 200 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 15.3mJ/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, these test blocks of after fixing 90 minutes.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 whisking appliance and prolong is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-epoxycyclohexyl methyl esters 1500 grams; Bisphenol A type epoxy resin (E-51) 300 grams; 3,3-[oxygen base dimethylene]-two [3-ethyl] trimethylene oxide 330 grams, polypropylene glycol diglycidyl ether diacrylate 600 grams; 1-hydroxy cyclohexyl phenylketone 90 grams, triaryl matte hexafluoro antimonate 180 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 14.1 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, these test blocks of after fixing 90 minutes.Record their warp factor CF (6)=-0.01, CF (11)=0.01.
Embodiment 5.
1. in the special 5000 milliliters glass there-necked flask of whisking appliance and prolong is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-epoxycyclohexyl methyl esters 1700 grams; Bisphenol A type epoxy resin (E-51) 400 grams; 3,3-[oxygen base dimethylene]-two [3-ethyl] trimethylene oxide 450 grams, polypropylene glycol diglycidyl ether diacrylate 200 grams; 1-hydroxy cyclohexyl phenylketone 100 grams, triaryl matte hexafluoro antimonate 150 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 15.7 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, these test blocks of after fixing 90 minutes.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 (10)
1. a polypropylene glycol diglycidyl ether diacrylate is characterized in that being made up of following raw material by the quality proportioning as the stereolithography rapid shaping photosensitive resin that prepolymer prepares:
10~70% polypropylene glycol diglycidyl ether diacrylate
5~75% epoxy resin
5~55% oxetane compounds
1~12% cationic initiator
1~10% free radical type Photoepolymerizationinitiater initiater.
2. stereolithography rapid shaping photosensitive resin according to claim 1 is characterized in that said epoxy resin is bisphenol A type epoxy resin, phenol aldehyde type epoxy resin, cycloaliphatic epoxy resin or claims one or more the mixture in the alicyclic epoxide compound.
3. stereolithography rapid shaping photosensitive resin according to claim 1 and 2 is characterized in that said 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. according to claim 1 or 4 described stereolithography rapid shaping photosensitive resins, it is characterized in that described oxetane compound is for preferably containing the organism of 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 initiator is salt compounded of iodine or sulfonium salt.
7. according to claim 1 or 6 described stereolithography rapid shaping photosensitive resins, it is characterized in that described cationic initiator is 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 free radical type Photoepolymerizationinitiater initiater carries out polymeric free radical type initiator for causing all unsaturated monomers that contain carbon-to-carbon double bond.
9. according to claim 1 or 8 described stereolithography rapid shaping photosensitive resins, it is characterized in that described free radical type Photoepolymerizationinitiater initiater is UVNUL MS-40, st-yrax dme, diphenyl antimony chloride ketone, 4-benzoyl--4
'-dimethyl diphenyl sulfide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy cyclohexyl phenylketone or 2, one or more mixtures in the 4-diethyl thioxanthone.
10. the preparation method of the described stereolithography rapid shaping of claim 1 photosensitive resin is characterized in that said material component and quality proportioning are mixed; Under 20~80 ℃ of temperature, stirred 5~120 minutes then, make it to become the transparent faint yellow uniform liquid.
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Cited By (7)
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CN102952257A (en) * | 2012-11-05 | 2013-03-06 | 南昌大学 | Method for preparing stereolithography rapid-prototyping photosensitive resin by adopting 1,4-cyclohexanedimethanol diglycidyl ether diacrylate as prepolymer |
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 |
CN106749987A (en) * | 2016-12-12 | 2017-05-31 | 中山大简高分子材料有限公司 | It is a kind of for the SLA photosensitive resin compositions of 3D printing and its application |
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 |
CN109438631A (en) * | 2018-10-22 | 2019-03-08 | 南昌大学 | A kind of high-precision and high heat distortion temperature stereolithography 3D printing photosensitive resin and preparation method thereof |
CN111892894A (en) * | 2017-01-25 | 2020-11-06 | 积水化学工业株式会社 | Sealing agent for liquid crystal display element, vertical conduction material, liquid crystal display element, and cured product |
CN112574366A (en) * | 2020-12-22 | 2021-03-30 | 杜晖 | Photosensitive resin, transparent mold for injection molding of photosensitive resin and injection molding method |
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Cited By (8)
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CN102952257A (en) * | 2012-11-05 | 2013-03-06 | 南昌大学 | Method for preparing stereolithography rapid-prototyping photosensitive resin by adopting 1,4-cyclohexanedimethanol diglycidyl ether diacrylate as prepolymer |
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 |
CN106749987A (en) * | 2016-12-12 | 2017-05-31 | 中山大简高分子材料有限公司 | It is a kind of for the SLA photosensitive resin compositions of 3D printing and its application |
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 |
CN111892894A (en) * | 2017-01-25 | 2020-11-06 | 积水化学工业株式会社 | Sealing agent for liquid crystal display element, vertical conduction material, liquid crystal display element, and cured product |
CN109438631A (en) * | 2018-10-22 | 2019-03-08 | 南昌大学 | A kind of high-precision and high heat distortion temperature stereolithography 3D printing photosensitive resin and preparation method thereof |
CN109438631B (en) * | 2018-10-22 | 2021-02-09 | 南昌大学 | High-precision and high-thermal-deformation-temperature stereolithography 3D printing photosensitive resin and preparation method thereof |
CN112574366A (en) * | 2020-12-22 | 2021-03-30 | 杜晖 | Photosensitive resin, transparent mold for injection molding of photosensitive resin and injection molding method |
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