CN105116686A - Photosensitive resin for 3D printing - Google Patents
Photosensitive resin for 3D printing Download PDFInfo
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- CN105116686A CN105116686A CN201510543808.9A CN201510543808A CN105116686A CN 105116686 A CN105116686 A CN 105116686A CN 201510543808 A CN201510543808 A CN 201510543808A CN 105116686 A CN105116686 A CN 105116686A
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Abstract
The invention discloses photosensitive resin for 3D printing. The photosensitive resin comprises the following components: oligomer, namely caprolactone modified urethane acrylate, an active diluent (namely mono-functional acrylate, dual-functional acrylate, multi-functional acrylate, a vinyl monomer, vinyl ether, methoxyl-containing mono-functional acrylate, carbamate-containing mono-functional acrylate or cyclic carbonate-containing mono-functional acrylate), and an ultraviolet initiator (namely, benzoin ether, 2,2-dimethyl alpha-hydroxyacetophenone or azide). Compared with the existing photosensitive resin for 3D printing, the photosensitive resin for 3D printing disclosed by the invention is low in cost and easy to popularize and apply; during use, a spraying head is unlikely to block, and a printed material is a three-dimensional printed material which is excellent in flexibility and mechanical performance.
Description
Technical field
The present invention relates to photosensitive resin composition, particularly a kind of 3D printing photosensitive resin.
Background technology
It is based on droplet ejection technology that photocuring 3D (three-dimensional) prints, use liquid photosensitive resin molded part, a kind of technique be cured with ultraviolet light, it by reaction-injection moulding together with the advantages of optical soliton interaction, substantially increase forming accuracy, and reduce costs.Shower nozzle moves back and forth along X-axis, and injection solid material and propping material form a layer cross section simultaneously, and use ultraviolet radiation-curable.Repeat this process, pile up layer by layer, support to obtain drip molding finally by aftertreatment removing.Based on this technology, the InVision series that the Eden series forming machine produced with OBJETGeometries company and 3DSystems company produce and ProJet series three-dimensional printer are for representative.The Eden series three-dimensional printer of OBJETGeometries company of Israel exploitation, supports resin by the photocuring entity of successively print liquid and photocuring, and ultraviolet light polymerization, after profiled member completes, finally remove propping material with hydraulic giant.Be wax and the photosensitive resin of employing hot shower nozzle injection melting at the 3DP of exploitation in 2003 by 3DSystems company, wherein wax is propping material, is removed by heat fused.
Photocuring blasting materials and photosensitive resin (UV ink-jet ink), existing market situation is that 3D printed photosensitive resin material price is high, limits applying of 3D printing.
Summary of the invention
The object of the invention is to overcome above-mentioned deficiency existing in prior art, a kind of new 3D printing photosensitive resin is provided.
In order to realize foregoing invention object, the invention provides following technical scheme:
A kind of 3D printing photosensitive resin, its raw material packet is containing following component:
Oligomer: polyether acrylate or hyperbranched polyester acrylic ester;
Reactive diluent: monofunctional acrylates's ester, bifunctional acrylate, multi-functional acrylate, vinyl monomer, vinyl ether, monofunctional acrylates's ester containing monofunctional acrylates's ester of methoxy end group, monofunctional acrylates's ester of amido-containing acid ester or cyclic carbonate ester;
Ultraviolet initiator: styrax ethers, benzophenone or triazo-compound;
Above-mentioned 3D printing photosensitive resin, its raw material preferably comprises:
Oligomer: caprolactone modification urethane acrylate;
Reactive diluent: 1,6-hexanediyl ester, isodecyl acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate;
Ultraviolet initiator: benzoin dimethylether or 2,2-dimethyl alpha-hydroxyacetophenone.
Above-mentioned 3D printing photosensitive resin, its raw material preferably comprises by weight:
Oligomer 50-70 part;
Reactive diluent 50-60 part;
Ultraviolet initiator 2-5 part.
Above-mentioned 3D printing photosensitive resin, its raw material also comprises auxiliary agent, as plastifier, thermal stabilizer, levelling agent.
Above-mentioned 3D printing photosensitive resin, its raw material is composed of the following components by weight:
Oligomer 50-70 part;
Reactive diluent 50-60 part;
Ultraviolet initiator 2-5 part;
Plastifier 1-8 part;
Thermal stabilizer 0.01-2 part;
Levelling agent 0.01-2 part.
Compared with prior art, beneficial effect of the present invention: 3D printing photosensitive resin of the present invention, cost more existing 3D printing photosensitive resin is low, is easy to apply; Not easily block shower nozzle in use, the material printed has the 3 D-printing material of excellent compliance and mechanical property.
Embodiment
Below in conjunction with test example and embodiment, the present invention is described in further detail.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on content of the present invention all belong to scope of the present invention.
Embodiment 1 one kinds of 3D printing photosensitive resins, its raw material is by weight, composed of the following components:
Oligomer: caprolactone modification urethane acrylate 55 parts;
Reactive diluent: 1,6-hexanediyl ester 40 parts;
Ultraviolet initiator: benzoin dimethylether 2 parts;
Plastifier: BBP(Butyl Benzyl Phthalate (BBP) 1 part;
Thermal stabilizer: 2,6-di-tert-butyl-4-methy phenol (BHT) 0.2 part;
Levelling agent: polyether-modified dimethyl siloxane 2 parts.
The levelling agent that this example adopts is the brand that Germany produces is Bi Ke BYK, and model is the polyether-modified dimethyl siloxane of BYK333.
Prepare this routine 3D printing photosensitive resin, the method that often can adopt by this area is carried out, such as, at 25 ~ 40 DEG C, feed composition can be uniformly mixed 15 ~ 30 minutes, obtains 3D printed photosensitive resin.
This routine 3D prints moderate with photosensitive resin viscosity, and photosensitivity is better, and its solidfied material volumetric shrinkage is little, and has better mechanical property and thermal behavior, specific as follows:
1) physicochemical property before solidification:
Security: the liquid resin nontoxic, nonflammable, volatility is little;
Surface tension: between 26-36mN/m;
Viscosity: viscosity is lower, during room temperature storage, viscosity is at about 30-300mPa.s;
PH value: between 7-8;
2) jet performance:
The form of drop: the drop size of injection is even, and the constant airspeed that drop is sprayed;
Water-based support photosensitive resin: rate of drying be suitable for, can not because rate of drying is too fast plug nozzle;
3) light-cured performance:
Laser curing velocity: have stronger absorption near 365nm, fast at the curing rate of uviol lamp;
Cure shrinkage: solid material cure shrinkage is low;
4) mechanical property after solidification and other performance:
Solid material: shore hardness more than 85, pulling strengrth is greater than 26MPa, and bending strength is greater than 50MPa, and breaking elongation is greater than 10%;
Propping material: the weight that solid material can be born, indeformable under load-bearing, do not compressed, support and easily remove, free from environmental pollution.
Embodiment 2 one kinds of 3D printing photosensitive resins, its raw material is by weight, composed of the following components:
Oligomer: caprolactone modification urethane acrylate 50 parts;
Reactive diluent: isodecyl acrylate 45.5 parts;
Ultraviolet initiator: 2,2-dimethyl alpha-hydroxyacetophenone 2 parts;
Plastifier: di-sec-octyl phthalate (DCP) 0.5 part;
Thermal stabilizer: 2,6-di-tert-butyl-4-methy phenol (BHT) 1 part;
Levelling agent: polyether-modified dimethyl siloxane 1 part.
Embodiment 3 one kinds of 3D printing photosensitive resins, its raw material is by weight, composed of the following components:
Oligomer: caprolactone modification urethane acrylate 50 parts;
Reactive diluent: pentaerythritol triacrylate 44.4 parts;
Ultraviolet initiator: benzoin dimethylether 2 parts;
Plastifier: di-sec-octyl phthalate (DCP) 2 parts;
Thermal stabilizer: 2,6-di-tert-butyl-4-methy phenol (BHT) 0.7 part;
Levelling agent: the polyether-modified dimethyl siloxane of levelling agent 0.9 part.
This routine plastifier, thermal stabilizer, levelling agent also can adopt other preparation conventional in industry.
Claims (6)
1. a 3D printing photosensitive resin, is characterized in that, its raw material packet is containing following component:
Oligomer: caprolactone modification urethane acrylate;
Reactive diluent: monofunctional acrylates's ester, bifunctional acrylate, multi-functional acrylate, vinyl monomer, vinyl ether, monofunctional acrylates's ester containing monofunctional acrylates's ester of methoxy end group, monofunctional acrylates's ester of amido-containing acid ester or cyclic carbonate ester;
Ultraviolet initiator: styrax ethers, 2,2-dimethyl alpha-hydroxyacetophenone or triazo-compounds.
2. 3D printing photosensitive resin according to claim 1, is characterized in that, its raw material packet is containing following component:
Oligomer: caprolactone modification urethane acrylate;
Reactive diluent: 1,6-hexanediyl ester, isodecyl acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate;
Ultraviolet initiator: benzoin dimethylether or 2,2-dimethyl alpha-hydroxyacetophenone.
3. 3D printing photosensitive resin according to claim 1 and 2, is characterized in that, by weight, its raw material packet contains:
Oligomer 50-70 part;
Reactive diluent 40-50 part;
Ultraviolet initiator 2-5 part.
4. 3D printing photosensitive resin according to claim 1 and 2, it is characterized in that, its raw material also comprises auxiliary agent.
5. 3D printing photosensitive resin according to claim 4, is characterized in that, described auxiliary agent is plastifier, thermal stabilizer and/or levelling agent.
6. 3D printing photosensitive resin according to claim 5, is characterized in that, by weight, its raw material is composed of the following components:
Oligomer 50-70 part;
Reactive diluent 40-50 part;
Ultraviolet initiator 2-5 part;
Plastifier 1-8 part;
Thermal stabilizer 0.01-1 part;
Levelling agent 0.01-1 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510543808.9A CN105116686A (en) | 2015-08-28 | 2015-08-28 | Photosensitive resin for 3D printing |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510543808.9A CN105116686A (en) | 2015-08-28 | 2015-08-28 | Photosensitive resin for 3D printing |
Publications (1)
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| CN105116686A true CN105116686A (en) | 2015-12-02 |
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| CN201510543808.9A Pending CN105116686A (en) | 2015-08-28 | 2015-08-28 | Photosensitive resin for 3D printing |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105785714A (en) * | 2016-03-30 | 2016-07-20 | 华中科技大学 | Photosensitive resin for 3D printing and preparation and application method thereof |
| CN105859956A (en) * | 2016-04-25 | 2016-08-17 | 江苏敦超电子科技有限公司 | Photosensitive resin for solid materials and preparation method thereof |
| CN105949881A (en) * | 2016-05-18 | 2016-09-21 | 江门市蓬江区文森装饰材料有限公司 | UV (ultraviolet) curing printing ink for 3D (three-dimensional) printing |
| CN107674149A (en) * | 2017-09-23 | 2018-02-09 | 江山海维科技有限公司 | A kind of preparation method of polyfunctionality acrylate containing strontium for photosensitive resin |
| CN108047386A (en) * | 2017-12-22 | 2018-05-18 | 深圳摩方新材科技有限公司 | It is a kind of for flexible photosensitive resin of 3D printing and preparation method thereof |
| CN108713033A (en) * | 2016-03-14 | 2018-10-26 | 麦克赛尔控股株式会社 | The manufacturing method of model timber-used composition, light chisel product and light chisel product |
| WO2020112496A1 (en) * | 2018-11-30 | 2020-06-04 | 3D Systems, Inc. | Inks for 3d printing having low polymerization shrinkage |
| CN113968738A (en) * | 2020-07-23 | 2022-01-25 | 中国科学院沈阳自动化研究所 | Ceramic precursor slurry for additive manufacturing and additive manufacturing process |
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| JPS61185522A (en) * | 1985-02-13 | 1986-08-19 | Nippon Kayaku Co Ltd | Novel urethane poly(meth)acrylate mixture and photo-setting resin composition containing same |
| CN101104724A (en) * | 2002-02-01 | 2008-01-16 | 纳托科株式会社 | Composition curable with actinic energy ray and use thereof |
| CN101437904A (en) * | 2006-04-25 | 2009-05-20 | 三菱丽阳株式会社 | Active energy ray-curable coating composition, and molded article having cured film of the composition |
| 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 |
| WO2015050398A1 (en) * | 2013-10-02 | 2015-04-09 | Samsung Electronics Co., Ltd. | Multi-color ink for 3d printing, 3d printer, and method of controlling the 3d printer |
-
2015
- 2015-08-28 CN CN201510543808.9A patent/CN105116686A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61185522A (en) * | 1985-02-13 | 1986-08-19 | Nippon Kayaku Co Ltd | Novel urethane poly(meth)acrylate mixture and photo-setting resin composition containing same |
| CN101104724A (en) * | 2002-02-01 | 2008-01-16 | 纳托科株式会社 | Composition curable with actinic energy ray and use thereof |
| CN101437904A (en) * | 2006-04-25 | 2009-05-20 | 三菱丽阳株式会社 | Active energy ray-curable coating composition, and molded article having cured film of the composition |
| 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 |
| WO2015050398A1 (en) * | 2013-10-02 | 2015-04-09 | Samsung Electronics Co., Ltd. | Multi-color ink for 3d printing, 3d printer, and method of controlling the 3d printer |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108713033A (en) * | 2016-03-14 | 2018-10-26 | 麦克赛尔控股株式会社 | The manufacturing method of model timber-used composition, light chisel product and light chisel product |
| CN108713033B (en) * | 2016-03-14 | 2021-06-15 | 麦克赛尔控股株式会社 | Composition for mold material, optical molded article, and method for producing optical molded article |
| CN105785714A (en) * | 2016-03-30 | 2016-07-20 | 华中科技大学 | Photosensitive resin for 3D printing and preparation and application method thereof |
| CN105859956A (en) * | 2016-04-25 | 2016-08-17 | 江苏敦超电子科技有限公司 | Photosensitive resin for solid materials and preparation method thereof |
| CN105949881A (en) * | 2016-05-18 | 2016-09-21 | 江门市蓬江区文森装饰材料有限公司 | UV (ultraviolet) curing printing ink for 3D (three-dimensional) printing |
| CN107674149A (en) * | 2017-09-23 | 2018-02-09 | 江山海维科技有限公司 | A kind of preparation method of polyfunctionality acrylate containing strontium for photosensitive resin |
| CN108047386A (en) * | 2017-12-22 | 2018-05-18 | 深圳摩方新材科技有限公司 | It is a kind of for flexible photosensitive resin of 3D printing and preparation method thereof |
| WO2020112496A1 (en) * | 2018-11-30 | 2020-06-04 | 3D Systems, Inc. | Inks for 3d printing having low polymerization shrinkage |
| US11370928B2 (en) | 2018-11-30 | 2022-06-28 | 3D Systems, Inc. | Inks for 3D printing having low polymerization shrinkage |
| US11897189B2 (en) | 2018-11-30 | 2024-02-13 | 3D Systems, Inc. | Inks for 3D printing having low polymerization shrinkage |
| CN113968738A (en) * | 2020-07-23 | 2022-01-25 | 中国科学院沈阳自动化研究所 | Ceramic precursor slurry for additive manufacturing and additive manufacturing process |
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Application publication date: 20151202 |
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