CN103246164A - Photosensitive resin for stereo lithography forming and preparation method thereof - Google Patents
Photosensitive resin for stereo lithography forming and preparation method thereof Download PDFInfo
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- CN103246164A CN103246164A CN2013102192001A CN201310219200A CN103246164A CN 103246164 A CN103246164 A CN 103246164A CN 2013102192001 A CN2013102192001 A CN 2013102192001A CN 201310219200 A CN201310219200 A CN 201310219200A CN 103246164 A CN103246164 A CN 103246164A
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Abstract
The invention discloses photosensitive resin for three-dimensional printing, which consists of the following components in percentage by mass: 60 to 80 percent of self-crosslinking acrylate monomer, 10 to 30 percent of acrylate copolymer, 0 to 10 percent of polyvinylpyrrolidone thickener and 1 to 4 percent of free radical type photopolymerization initiator. Relative to conventional commoditized photosensitive resin, the photosensitive resin prepared by the invention has no toxicity unless a user carelessly intakes the photosensitive resin into the body, totally has no pungent smell, can be used for the home environment and has no toxicity or pollution for the aquatic environment. after visible light stereo lithography forming, the photosensitive resin has the characteristics that a formed part has no toxicity, has high accuracy and good environmental compatibility and is easily subjected to subsequent processes of coloring, spraying and the like; and the photosensitive resin completely can be used for lithography rapid forming of artware, jewelries, toys and the like.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of photosensitive resin of special formulation, relate in particular to a kind of home environment that is used safely in, 3 D-printing (stereolithography) photosensitive resin that can be caused by visible light and preparation method thereof.
Background technology
3 D-printing is not to be fresh technology, and this thought originates from the U.S. in 19 end of the centurys, and is developed and promote in military domain in the eighties in 20th century, is called rapid shaping technique again.Our the applied 3 D-printing technology differentiation that is rapid shaping technique in fact at present.So-called 3 D-printing is made object model at three-dimensional planar exactly, specifically be to be designed to source with electronic 3-D model, divide layer scattering by software with model, make machine and from software, obtain virtual blueprint with the foundation as printing of arranging of their preface, and the material of printing is deposited in to generate and finishes up to the layering of material bonding agent on the platform, finally is printed moulding up to three-dimensional model.
Stereolithography is the most ripe 3 D-printing technology, has fast, the precision advantages of higher of shaping speed, its essence is a kind of superimposed type advanced manufacturing technology, cardinal principle be with the object of required moulding by the digital model discretize, make required profiled member by the orderly accumulation of material again.At first the three-dimensional model of the article that will build is converted into digital model by computer-aided design (CAD) (CAD) and saves as general three-dimensional Standard File Formats such as STL, with delamination software that three-dimensional model is discrete in height Z direction, form a series of certain thickness thin slices that have, utilize laser beam under computer control, selectively to solidify or a certain zone that bonds, thereby form an aspect of constituent part entity, so successively pile up three-dimensional prototype entity of formation.
Light-cured resin is the core technology that realizes stereolithography, up to now, has successfully developed the different light-cured resin that is used for stereolithography of numerous performances both at home and abroad.Present commercial stereolithography photosensitive resin all is with the free radical type photosensitive resin as prepolymer such as epoxy acrylate or urethane acrylate, as 2100,2110,3100,3110 of 5091,5131,5149 and Dupont company of Ciba-Geigy Cibatool company research and development, Huntsman SL5530HT, DSM Somos ProtoTherm14120, DSM Somos19120, SPR9000, SPR9100 etc.The location of three-dimensional printer in the market is research and development equipment always, is applied in the front end of new product development, is used for doing the palm model.Therefore, the installation client above 90% is industry (commercialization) client on the present market.Civilian client (individual three-dimensional printer client, the three-dimensional printer client of family) though quantity increasing progressively, installation amount still is considerably less.The prepolymer of the employed stereolithography photosensitive resin of these commercial three-dimensional printers is mainly based on epoxy resin, acrylate is auxilliary, belong to free radical or kation initiated polymerization type photosensitive resin, expensive, prepolymer has big toxicity, be mainly used in industrial rapid prototyping, operating personnel need be equipped with special labor and social security equipment.And, owing to contain environmentally hazardous industrial chemicals usually in the prepolymer, when clearing up profiled member and handling the resin of not using up, needing special chemical waste treatment scheme and equipment, can not use at home fully.
Summary of the invention
At existing stereolithography photosensitive resin high toxicity, harm environment, can not family expenses shortcoming, the object of the present invention is to provide prescription and the preparation method of the stereolithography photosensitive resin of a kind of nontoxic, environmental protection for family expenses, safety, above-mentioned resin can enter the household application market in the high-precision three-dimensional printing and play the critical material effect, be the gordian technique that realizes family expenses stereolithography three-dimensional printer, can satisfy existing photosensitive resin be beyond one's reach environmental protection and security requirement.
Purpose of the present invention is realized by following technical scheme:
A kind of 3 D-printing photosensitive resin of safety and environmental protection is 100% in described photosensitive resin gross mass, and wherein each component and quality percentage composition thereof are as follows:
Wherein the self-crosslinking acrylic ester monomer is preferred
Polyglycol (200) diacrylate
Polyglycol (400) diacrylate
Polyglycol (600) diacrylate
Wherein acrylate copolymer is preferred
Hydroxyethyl methylacrylate
1,6-hexanediyl ester
The free radical type Photoepolymerizationinitiater initiater is preferred
(2,4,6-trimethylbenzoyl) diphenyl phosphine oxide
Two (2,4, the 6-trimethylbenzene formyl) phosphine oxides of phenyl
Preparation method's step of described photosensitive resin is as follows:
(1) be that free radical type Photoepolymerizationinitiater initiater, self-crosslinking acrylic ester monomer, the acrylate copolymer of 1-4:60-80:10-30 evenly mixes by mass ratio;
(2) add in the potpourri that step (1) obtains that to make its massfraction be the polyvinylpyrrolidone thickening agent of 0-10%, even matter stirred 1～45 minute, and described thickening agent is fully dissolved, and kept in Dark Place, and namely obtained photosensitive resin of the present invention.
The free radical type Photoepolymerizationinitiater initiater is two (2,4, the 6-trimethylbenzene formyl) phosphine oxides of (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide or phenyl in the described step 1; The self-crosslinking acrylic ester monomer is polyglycol (200) diacrylate, polyglycol (400) diacrylate or polyglycol (600) diacrylate; Acrylate copolymer is hydroxyethyl methylacrylate or 1,6-hexanediyl ester;
Even matter stirs and adopts even matter stirring machine in the described step 2.
Ultimate principle of the present invention is as follows:
For making photosensitive resin be used safely in domestic environment, traditional high toxicity monomer, such as epoxy resin, phenolics, acrylamide, polyurethane etc. all can not use.Realize light initiating polymerizing reaction then optional polymerization single polymerization monomer only be acrylic compounds.And domestic environment also has specific (special) requirements to penetrating odor, and is nontoxic and that respiratory tract is not had the monomer of influence is very few in acrylic monomer, and the monomer that may be used for family expenses through screening only be propylene acid alcohol and acrylic acid ethylene glycol, three alcohols.The polymerization of acrylate is that two keys are opened the polymerization that becomes singly-bound, shrinks greatlyyer, so must regulate the ratio of acrylic acid ester bond and crosslinking points by MOLECULE DESIGN, makes resin after the curing reach the physical strength of needs, has less shrinkage ratio simultaneously.
In addition, for satisfying the family expenses requirement, the present invention also selects initiating agent.Tradition is the light-cured resin overwhelming majority caused by ultraviolet light, and the common power of ultraviolet source is bigger, and cost is very high, for family expenses safety inadequately.Therefore, the present invention has selected visible royal purple light (wavelength 405nm) is had the initiating agent of better response especially, uses all solid state light source, satisfies the requirement of family expenses low cost, high security.
Useful technique effect of the present invention is with respect in the past commercialization photosensitive resin, and avirulence has no irritating odor fully unless the photosensitive resin of the present invention's preparation is taken in the body accidentally, can be used for domestic environment, to aquatic environment nonhazardous and pollution.Behind the visible light stereolithography, its characteristics are that profiled member is nontoxic, precision is high, Environmental compatibility is good, use all solid state light source, satisfy family expenses low cost, high security, be easy to paint and subsequent technique etc. such as spray, can be used for the photoetching rapid shaping of handicraft, jewellery, toy etc. fully.
Embodiment
Below in conjunction with specific embodiment in detail the present invention is described in detail, but is not limited thereto.
Embodiment 1
In 1000 milliliters of plastic beakers, add phenyl two (2,4,6-trimethylbenzene formyl) phosphine oxide 10 grams, polyglycol (200) diacrylate 600 grams, hydroxyethyl methylacrylate 300 grams, mix, until becoming the transparent faint yellow uniform liquid, add polyvinylpyrrolidone 90 grams, homogeneous stirring machine working head is stretched in the beaker, homogeneous stirred 10 minutes, obtained the faint yellow uniform liquid of proper viscosity (about 500cp), and gained is photosensitive resin.
Utilizing power is that the 405nm wavelength visible-light curing case of 500 milliwatts solidified test block 10 minutes.According to ASTM D2240, ASTM D790, ASTM D638 and ASTM D648 standard method of test, record shore hardness 70D respectively, pulling strengrth 34MPa, stretch modulus 1912MPa, breaking elongation 2.8%.
According to GB/T18883-2002 IAQ (indoor air quality) standard, GB50325-2001 civil building engineering environmental contaminants control codes and standards to uncured and solidify after resin test formaldehyde, benzene, ammonia, toluene, dimethylbenzene, TVOC are all up to standard, can use safely in indoor environment.
Carry out water-quality test according to the waste water of GB/T5750.7-2006 water quality monitoring standard after to cleaning components, total organic carbon, petroleum-type, conductivity are all up to standard, and waste water can directly enter the urban sewage system.
Embodiment 2
In 1000 milliliters of plastic beakers, add phenyl two (2,4,6-trimethylbenzene formyl) phosphine oxide 40 grams, polyglycol (400) diacrylate 700 grams, hydroxyethyl methylacrylate 200 grams, mix, until becoming the transparent faint yellow uniform liquid, add polyvinylpyrrolidone 60 grams, homogeneous stirring machine working head is stretched in the beaker, homogeneous stirred 10 minutes, obtained the faint yellow uniform liquid of proper viscosity (about 100cp), and gained is photosensitive resin.
Utilizing power is that the 405nm wavelength visible-light curing case of 500 milliwatts solidified test block 10 minutes.According to ASTM D2240, ASTM D790, ASTM D638 and ASTM D648 standard method of test, record shore hardness 50D respectively, pulling strengrth 40MPa, stretch modulus 1600MPa, breaking elongation 2.9%.
According to GB/T18883-2002 IAQ (indoor air quality) standard, GB50325-2001 civil building engineering environmental contaminants control codes and standards to uncured and solidify after resin test formaldehyde, benzene, ammonia, toluene, dimethylbenzene, TVOC are all up to standard, can use safely in indoor environment.
Carry out water-quality test according to the waste water of GB/T5750.7-2006 water quality monitoring standard after to cleaning components, total organic carbon, petroleum-type, conductivity are all up to standard, and waste water can directly enter the urban sewage system.
Embodiment 3
In 1000 milliliters of plastic beakers, add (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide 10 grams; polyglycol (600) diacrylate 600 grams; 1,6-hexanediyl ester, 300 grams mix; until becoming the transparent faint yellow uniform liquid; add polyvinylpyrrolidone 90 grams, homogeneous stirring machine working head is stretched in the beaker, homogeneous stirred 10 minutes; obtain the faint yellow uniform liquid of proper viscosity (about 500cp), gained is photosensitive resin.
Utilizing power is that the 405nm wavelength visible-light curing case of 500 milliwatts solidified test block 10 minutes.According to ASTM D2240, ASTM D790, ASTM D638 and ASTM D648 standard method of test, record shore hardness 75D respectively, pulling strengrth 40MPa, stretch modulus 1750MPa, breaking elongation 1.8%.
According to GB/T18883-2002 IAQ (indoor air quality) standard, GB50325-2001 civil building engineering environmental contaminants control codes and standards to uncured and solidify after resin test formaldehyde, benzene, ammonia, toluene, dimethylbenzene, TVOC are all up to standard, can use safely in indoor environment.
Carry out water-quality test according to the waste water of GB/T5750.7-2006 water quality monitoring standard after to cleaning components, total organic carbon, petroleum-type, conductivity are all up to standard, and waste water can directly enter the urban sewage system.
Embodiment 4
In 1000 milliliters of plastic beakers, add (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide 30 grams; polyglycol (600) diacrylate 800 grams; 1,6-hexanediyl ester, 100 grams mix; until becoming the transparent faint yellow uniform liquid; add polyvinylpyrrolidone 70 grams, homogeneous stirring machine working head is stretched in the beaker, homogeneous stirred 10 minutes; obtain the faint yellow uniform liquid of proper viscosity (about 120cp), gained is photosensitive resin.
Utilizing power is that the 405nm wavelength visible-light curing case of 500 milliwatts solidified test block 10 minutes.According to ASTM D2240, ASTM D790, ASTM D638 and ASTM D648 standard method of test, record shore hardness 65D respectively, pulling strengrth 45MPa, stretch modulus 1950MPa, breaking elongation 2.1%.
According to GB/T18883-2002 IAQ (indoor air quality) standard, GB50325-2001 civil building engineering environmental contaminants control codes and standards to uncured and solidify after resin test formaldehyde, benzene, ammonia, toluene, dimethylbenzene, TVOC are all up to standard, can use safely in indoor environment.
Carry out water-quality test according to the waste water of GB/T5750.7-2006 water quality monitoring standard after to cleaning components, total organic carbon, petroleum-type, conductivity are all up to standard, and waste water can directly enter the urban sewage system.
Embodiment 5
In 1000 milliliters of plastic beakers, add (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide 40 grams; polyglycol (600) diacrylate 700 grams; 1,6-hexanediyl ester, 200 grams mix; until becoming the transparent faint yellow uniform liquid; add polyvinylpyrrolidone 60 grams, homogeneous stirring machine working head is stretched in the beaker, homogeneous stirred 10 minutes; obtain the faint yellow uniform liquid of proper viscosity (about 60cp), gained is photosensitive resin.
Utilizing power is that the 405nm wavelength visible-light curing case of 500 milliwatts solidified test block 10 minutes.According to ASTM D2240, ASTM D790, ASTM D638 and ASTM D648 standard method of test, record shore hardness 65D respectively, pulling strengrth 43MPa, stretch modulus 1850MPa, breaking elongation 1.9%.
According to GB/T18883-2002 IAQ (indoor air quality) standard, GB50325-2001 civil building engineering environmental contaminants control codes and standards to uncured and solidify after resin test formaldehyde, benzene, ammonia, toluene, dimethylbenzene, TVOC are all up to standard, can use safely in indoor environment.
Carry out water-quality test according to the waste water of GB/T5750.7-2006 water quality monitoring standard after to cleaning components, total organic carbon, petroleum-type, conductivity are all up to standard, and waste water can directly enter the urban sewage system.
Above-described embodiment is every for the preferable enforcement of the present invention; but embodiments of the present invention are not restricted to the described embodiments; the change of doing under spiritual essence of the present invention and the principle in other any not north, modification, substitute, combination, simplify; all should be the substitute mode of equivalence, all will be considered as within protection scope of the present invention.
Claims (6)
1. photosensitive resin that is used for 3 D-printing is characterized in that being respectively 60～80% self-crosslinking acrylic ester monomer, 10～30% acrylate copolymer, 0～10% polyvinylpyrrolidone thickening agent and 1～4% free radical type Photoepolymerizationinitiater initiater by massfraction forms.
2. the photosensitive resin for 3 D-printing according to claim 1 is characterized in that described self-crosslinking acrylic ester monomer is polyethyleneglycol diacrylate, and wherein the mean molecular weight of polyglycol is 200,400 or 600.
3. the photosensitive resin for 3 D-printing according to claim 1 is characterized in that described acrylate copolymer is hydroxyethyl methylacrylate or 1,6-hexanediyl ester.
4. free radical type Photoepolymerizationinitiater initiater according to claim 1 is two (2,4, the 6-trimethylbenzene formyl) phosphine oxides of (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide or phenyl.
5. a method for preparing the described photosensitive resin for 3 D-printing of any claim among the claim 1-4 comprises
Step 1: be that free radical type Photoepolymerizationinitiater initiater, self-crosslinking acrylic ester monomer, the acrylate copolymer of 1-4:60-80:10-30 evenly mixes by mass ratio;
Step 2: add in the potpourri that step 1 obtains that to make its massfraction be the polyvinylpyrrolidone thickening agent of 0-10%, even matter stirred 1～45 minute, and described thickening agent is fully dissolved, and kept in Dark Place, and namely obtained the photosensitive resin for 3 D-printing.
6. the method for the photosensitive resin for the preparation of 3 D-printing according to claim 5, it is characterized in that the free radical type Photoepolymerizationinitiater initiater is (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide or phenyl two (2 in the step 1,4,6-trimethylbenzene formyl) phosphine oxide; The self-crosslinking acrylic ester monomer is polyethyleneglycol diacrylate, wherein the mean molecular weight of polyglycol is 200,400 or 600; Acrylate copolymer is hydroxyethyl methylacrylate or 1,6-hexanediyl ester.
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| CN103941543A (en) * | 2014-03-27 | 2014-07-23 | 沈阳巧时器美科技有限公司 | Photosensitive resin composition based on polylactide polyol, preparation method thereof and photosensitive resin |
| CN104109328A (en) * | 2014-06-23 | 2014-10-22 | 东莞智维立体成型股份有限公司 | Photocuring wax material used for 3D printing |
| CN104181773A (en) * | 2014-07-22 | 2014-12-03 | 北京金达雷科技有限公司 | Photosensitive resin for laser selective metallization, preparation method and activation method |
| CN104293116A (en) * | 2014-09-22 | 2015-01-21 | 南京航空航天大学 | Photo-curable three-dimensional printing material as well as preparation method and application thereof |
| CN104710548A (en) * | 2014-01-03 | 2015-06-17 | 刘毓海 | 3D printing core material |
| KR20160101997A (en) * | 2013-12-18 | 2016-08-26 | 이네오스 스티롤루션 그룹 게엠베하 | Moulding compositions based on vinylaromatic copolymers for 3d printing |
| CN105968240A (en) * | 2015-03-10 | 2016-09-28 | 郑正元 | Photo-curable resin composition for three-dimensional printing and three-dimensional printing system |
| CN107090063A (en) * | 2017-06-22 | 2017-08-25 | 广东恒大新材料科技有限公司 | A kind of photocuring 3D printing photosensitive resin composition |
| CN110003380A (en) * | 2019-03-19 | 2019-07-12 | 华中科技大学 | A kind of photosensitive resin preparation, forming and driving method for 4D printing |
| CN112778881A (en) * | 2021-01-06 | 2021-05-11 | 阜阳师范大学 | Epoxy acrylate ultraviolet curing material and preparation method thereof |
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| US10815367B2 (en) | 2013-12-18 | 2020-10-27 | Ineos Styrolution Group Gmbh | Moulding compositions based on vinylaromatic copolymers for 3D printing |
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| CN104109328A (en) * | 2014-06-23 | 2014-10-22 | 东莞智维立体成型股份有限公司 | Photocuring wax material used for 3D printing |
| CN104181773A (en) * | 2014-07-22 | 2014-12-03 | 北京金达雷科技有限公司 | Photosensitive resin for laser selective metallization, preparation method and activation method |
| CN104293116A (en) * | 2014-09-22 | 2015-01-21 | 南京航空航天大学 | Photo-curable three-dimensional printing material as well as preparation method and application thereof |
| CN105968240A (en) * | 2015-03-10 | 2016-09-28 | 郑正元 | Photo-curable resin composition for three-dimensional printing and three-dimensional printing system |
| CN107090063B (en) * | 2017-06-22 | 2019-05-24 | 广东恒大新材料科技有限公司 | A kind of photocuring 3D printing photosensitive resin composition |
| CN107090063A (en) * | 2017-06-22 | 2017-08-25 | 广东恒大新材料科技有限公司 | A kind of photocuring 3D printing photosensitive resin composition |
| CN110003380A (en) * | 2019-03-19 | 2019-07-12 | 华中科技大学 | A kind of photosensitive resin preparation, forming and driving method for 4D printing |
| CN112778881A (en) * | 2021-01-06 | 2021-05-11 | 阜阳师范大学 | Epoxy acrylate ultraviolet curing material and preparation method thereof |
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Application publication date: 20130814 |