CN105175645A - Three-dimensional printing photosensitive resin material containing macromelecular elastomers and preparation method - Google Patents
Three-dimensional printing photosensitive resin material containing macromelecular elastomers and preparation method Download PDFInfo
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- CN105175645A CN105175645A CN201510604989.1A CN201510604989A CN105175645A CN 105175645 A CN105175645 A CN 105175645A CN 201510604989 A CN201510604989 A CN 201510604989A CN 105175645 A CN105175645 A CN 105175645A
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Abstract
The invention belongs to the field of three-dimensional printing materials, and discloses a three-dimensional printing photosensitive resin material containing macromelecular elastomers and a preparation method. The resin material is prepared by 1%-5% of mixed photoinitiators, 8%-18% of methacrylic acid borneol esters, 1%-7% of N-vinylpyrrolidone, 30%-50% of the macromelecular elastomers, 10%-25% of 1,4-cyclohexyl methanol divinyl ethers and 10%-30% of ethyoxyl bisphenol A di-acrylic ester. According to the resin material, the elastic macromolecular macromonomers which take isoprene as the first block and ethylene oxide as the second block and are provided with end groups and vinyl groups are formed by taking phenyllithium containing double bonds as the initiators through anionic polymerization; a new direction is brought for a photocuring forming technology through the molecular design and synthesis technique; the toughness of the three-dimensional printing photosensitive resin is further improved by adding the macromelecular elastomers.
Description
Technical field
The invention belongs to 3D printed material technical field, be specifically related to a kind of containing macromole elastomeric 3D printed photosensitive resin material and preparation method thereof.
Background technology
Utilize light rapid shaping, manufacturing 3D printed material, is the state-of-the-art technology of rising in recent years, and it is extensive that it has material source, the advantage that shaping speed is fast.
Print in macromolecular material at use photocureable rapid shaping 3D, people start to find gradually, because material fragility and the low problem of mechanical strength, constrain material to real prototype or directly apply as product, the moulding product printed at present can only as model or product design, or the purposes of discovery techniques scheme in medical treatment, still can not directly as spendable product introduction daily life or industry, other department of national defence and some national economy.
This direct consequence is, have impact on use and the popularization of 3D printed material, limits 3D printed material technical superiority, therefore, solve the brittleness problems of polymer 3D printed material, be directly make macromolecular material enter 3D printing market, and directly become the key of operable product.
Analyze existing smooth rapid prototyping material, subject matter is that the toughness of material and elasticity can not meet actual requirement, and curing speed is faster, and the double bond number of needs is more, thus makes material produce contraction in the curing process, and mechanical property significantly reduces.
The structure of material fragility and material has close relationship, and mainly current used material is because of after Seterolithography, is difficult to be discharged because shrink the stress produced, and causes slip ability between macromolecular chain to weaken.
Elastomer material, has the ability of good release stress, the material especially containing double bond between some molecular chains, and in the macromolecular material in the past used, synthetic polyisoprene elasticity and deformation performance excellence, can discharge internal stress during solidification to greatest extent.But isoprene is as elastomeric material, owing to not having the double bond that can cause, simultaneously due to nonpolar problem, poor with current Seterolithography material compatibility, there will be phase-splitting and affects its mechanical property.
The present invention is by directly using the phenyl lithium containing double bond to be initiator, eliminate the difficult problem that the later stage connects double bond, the elastic polymer polymeric monomer that formation is A block with isoprene, oxyethane is B block, because containing terminal ethylenic base, ultraviolet light polymerization can be directly used in, reduce production cost to a great extent, improve efficiency, also do not relate in the prior art.
Summary of the invention
Technical problem: the object of the invention is, for solving the technical problems such as the toughness existed at present is not good, to provide a kind of containing macromole elastomeric 3D printed photosensitive resin material, 3D printed material can be made directly to carry out formed product.
Technical scheme: for achieving the above object, the technical solution used in the present invention is:
A kind of containing macromole elastomeric 3D printed photosensitive resin material, content is by component by mass percentage: mixed light initiator is 1-5%; Methacrylic acid norbornene ester is 8-18%; NVP is 1-7%; Macromole elastomerics is 30-50%; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 0-25%; Diethoxy dihydroxyphenyl propane two propylene is 10-30% composition.
Wherein said mixed light initiator, be made up of light trigger 1173, light trigger 369 and tertiary amine-type benzoic ether, its mass ratio is light trigger 1173: light trigger 369: tertiary amine-type benzoic ether=1:1:3, and wherein the molecular structure of tertiary amine-type benzoic ether is:
Wherein, R group is the alkyl containing 1-7 carbon atom, comprises the isomers gone out by alkyl derivative.
Described macromole elastomerics is single ethene macromonomer, namely with the phenyl lithium containing double bond for initiator, by anionoid polymerization isoprene, being formed with isoprene is that A block, oxyethane have an elastic polymer polymeric monomer of terminal ethylenic base for B block.
The molecular structure of the described phenyl lithium containing double bond is:
The molecular structure of described single ethene macromonomer is:
Wherein, n>m, n:m=1.5:1, n=15-45, m=10-30, its molecular weight is 1000-10000.
A kind of preparation method containing macromole elastomeric 3D printed photosensitive resin material of the present invention, comprises the steps:
(1) macromole elastomerics is prepared: according to the basic step of anionoid polymerization, take toluene as solvent, be sequentially added into containing lithium initiator and isoprene, at 90-100 DEG C of temperature, react 2h be down to room temperature, add oxyethane liquid, 50-70 DEG C of reaction 1h, is (4-8) containing the mass ratio of lithium initiator, isoprene, oxyethane at wherein said toluene: (0.5-1): 1:1;
(2) content takes each raw material of composition photosensitive resin material by mass percentage, and be placed on stirrer for mixing, with the rotating speed of 500r/min, mix and blend 1h, obtains photosensitive resin material;
(3) step (2) being obtained photosensitive resin material is applied on sheet glass, and smearing thickness is 1-5 μm, and under ultraviolet source, irradiation 10-30 solidifies second, and it is 300-500nm that photo solidification machine arranges wavelength.
Advantage of the present invention and beneficial effect be mainly:
(1) the present invention is initiator owing to directly using containing the phenyl lithium of double bond, and the elastic polymer polymeric monomer that to be formed with isoprene be A block, oxyethane is B block, because of containing terminal ethylenic base, so can be directly used in ultraviolet light polymerization;
(2) material of the present invention after tested, and its tensile strength is maximum reaches 14.98MPa, and elongation at break is 82% to the maximum, and density is 1.58g/cm
3(25 DEG C);
(3) the present invention utilizes molecular designing and synthesising skill, and will originally be difficult to the monomer connected, be connected on any position of polymer, this can be Stereolithography technology and opens up new direction.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below enumerating embodiment and the present invention is described in further detail.It will be appreciated by those skilled in the art that described embodiment only understands the present invention for helping, being not intended to limit the present invention.
Embodiment 1
A kind of containing macromole elastomeric 3D printed photosensitive resin material, be made up of following component by mass percentage: mixed light initiator 1%; Methacrylic acid norbornene ester 8%; NVP 1%; Macromole elastomerics 50%; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 20%; Diethoxy dihydroxyphenyl propane two propylene 20%.
Wherein, the R in tertiary amine-type benzoate structure formula is methyl.
Above-mentioned one contains macromole elastomeric 3D printed photosensitive resin material, and preparation method is as follows:
(1) the elastomeric preparation of macromole: according to the basic step of anionoid polymerization, take toluene as solvent, be sequentially added into containing lithium initiator and isoprene, at 90-100 DEG C of temperature, react 2h be down to room temperature, add oxyethane liquid, 50-70 DEG C of reaction 1h discharging, is (4-8) containing the mass ratio of lithium initiator, isoprene, oxyethane at described toluene: (0.5-1): 1:1;
(2) methacrylic acid norbornene ester 8g is taken respectively; NVP 1g; Macromole elastomerics 50g; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 20g; Diethoxy dihydroxyphenyl propane two propylene 20g, at stirrer for mixing 1h, stirring velocity is 500r/min, light trigger 1173,369 and tertiary amine-type benzoic ether 0.2g, 0.2g, 0.6g is added respectively under light protected environment, be uniformly mixed, standing 15min is applied on sheet glass, and smearing thickness is 1-5 μm, is that under the ultraviolet source of 300-500nm, irradiation 10-30 solidifies second at wavelength.
The effect of the present embodiment: can obtain through electronic universal drawing machine and fluid density test conventional method: tensile strength is 11.53MPa, and elongation at break is 60%, and density is 0.92g/cm3 (25 DEG C).
Embodiment 2
A kind of containing macromole elastomeric 3D printed photosensitive resin material, composed as follows: mixed light initiator 4%; Methacrylic acid norbornene ester 18%; NVP 1%; Macromole elastomerics 30%; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 22%; Diethoxy dihydroxyphenyl propane two propylene 25%.
Wherein, the R in tertiary amine-type benzoate structure formula is ethyl.
Above-mentioned one contains macromole elastomeric 3D printed photosensitive resin material, and preparation method is as follows:
(1) the elastomeric preparation of macromole: with embodiment 1;
(2) methacrylic acid norbornene ester 18g is taken respectively; NVP 1g; Macromole elastomerics 30g; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 22g; Diethoxy dihydroxyphenyl propane two propylene 25g, at stirrer for mixing 1h, stirring velocity is 500r/min, light trigger 1173,369 and tertiary amine-type benzoic ether 0.8g, 0.8g, 2.4g is added respectively under light protected environment, be uniformly mixed, standing 15min is applied on sheet glass, and smearing thickness is 1-5 μm, is that under the ultraviolet source of 300-500nm, irradiation 10-30 solidifies second at wavelength.
The present embodiment effect: can obtain through electronic universal drawing machine and fluid density test conventional method: tensile strength is 11.08MPa, and elongation at break is 55%, and density is 1.08g/cm3 (25 DEG C).
Embodiment 3
A kind of containing macromole elastomeric 3D printed photosensitive resin material, composed as follows: mixed light initiator 5%; Methacrylic acid norbornene ester 13%; NVP 7%; Macromole elastomerics 40%; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 10%; Diethoxy dihydroxyphenyl propane two propylene 25%.
Wherein, the R in tertiary amine-type benzoate structure formula is the tertiary butyl.
Above-mentioned one contains macromole elastomeric 3D printed photosensitive resin material, and its preparation method is as follows:
(1) the elastomeric preparation of macromole: with embodiment 1;
(2) methacrylic acid norbornene ester 13g is taken respectively; NVP 7g; Macromole elastomerics 40g; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 10g; Diethoxy dihydroxyphenyl propane two propylene 25g, at stirrer for mixing 1h, stirring velocity is 500r/min, light trigger 1173,369 and tertiary amine-type benzoic ether 1g, 1g, 3g is added respectively under light protected environment, be uniformly mixed, standing 15min is applied on sheet glass, and smearing thickness is 1-5 μm, is that under the ultraviolet source of 300-500nm, irradiation 10-30 solidifies second at wavelength.
The effect of the present embodiment: can obtain through electronic universal drawing machine and fluid density test conventional method: tensile strength is 12.30MPa, and elongation at break is 48%, and density is 1.23g/cm3 (25 DEG C).
Embodiment 4
A kind of containing macromole elastomeric 3D printed photosensitive resin material, composed as follows: mixed light initiator 5%; Methacrylic acid norbornene ester 12%; NVP 5%; Macromole elastomerics 38%; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 10%; Diethoxy dihydroxyphenyl propane two propylene 30%.
Wherein, the R in tertiary amine-type benzoate structure formula is sec.-propyl.
Above-mentioned one contains macromole elastomeric 3D printed photosensitive resin material, and its preparation method is as follows:
(1) the elastomeric preparation of macromole: with embodiment 1;
(2) methacrylic acid norbornene ester 12g is taken respectively; NVP 5g; Macromole elastomerics 38g; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 10g; Diethoxy dihydroxyphenyl propane two propylene 30g, at stirrer for mixing 1h, stirring velocity is 500r/min, light trigger 1173,369 and tertiary amine-type benzoic ether 1g, 1g, 3g is added respectively under light protected environment, be uniformly mixed, standing 15min is applied on sheet glass, and smearing thickness is 1-5 μm, is that under the ultraviolet source of 300-500nm, irradiation 10-30 solidifies second at wavelength.
The present embodiment effect: can obtain through electronic universal drawing machine and fluid density test conventional method: tensile strength is 13.87MPa, and elongation at break is 78%, and density is 1.15g/cm
3(25 DEG C).
Embodiment 5
A kind of containing macromole elastomeric 3D printed photosensitive resin material, composed as follows: mixed light initiator 4%; Methacrylic acid norbornene ester 14%; NVP 5%; Macromole elastomerics 42%; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 25%; Diethoxy dihydroxyphenyl propane two propylene 10%.
Wherein, the R in tertiary amine-type benzoate structure formula is heptyl.
Above-mentioned one contains macromole elastomeric 3D printed photosensitive resin material, and its preparation method is as follows:
(1) the elastomeric preparation of macromole: with embodiment 1;
(2) methacrylic acid norbornene ester 14g is taken respectively; NVP 5g; Macromole elastomerics 42g; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 25g; Diethoxy dihydroxyphenyl propane two propylene 10g, at stirrer for mixing 1h, stirring velocity is 500r/min, light trigger 1173,369 and tertiary amine-type benzoic ether 0.8g, 0.8g, 2.4g is added respectively under light protected environment, be uniformly mixed, standing 15min is applied on sheet glass, and smearing thickness is 1-5 μm, is that under the ultraviolet source of 300-500nm, irradiation 10-30 solidifies second at wavelength.
The present embodiment effect: can obtain through electronic universal drawing machine and fluid density test conventional method: tensile strength is 14.21MPa, and elongation at break is 72%, and density is 1.58g/cm3 (25 DEG C).
Embodiment 6
A kind of containing macromole elastomeric 3D printed photosensitive resin material, composed as follows: mixed light initiator 4%; Methacrylic acid norbornene ester 15%; NVP 1%; Macromole elastomerics 40%; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 12%; Diethoxy dihydroxyphenyl propane two propylene 28%.
Wherein, the R in tertiary amine-type benzoate structure formula is propyl group.
Above-mentioned one contains macromole elastomeric 3D printed photosensitive resin material, and its preparation method is as follows:
(1) the elastomeric preparation of macromole: with embodiment 1;
(2) methacrylic acid norbornene ester 15g is taken respectively; NVP 1g; Macromole elastomerics 40g; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 12g; Diethoxy dihydroxyphenyl propane two propylene 28g, at stirrer for mixing 1h, stirring velocity is 500r/min, light trigger 1173,369 and tertiary amine-type benzoic ether 0.8g, 0.8g, 2.4g is added respectively under light protected environment, be uniformly mixed, standing 15min is applied on sheet glass, and smearing thickness is 1-5 μm, is that under the ultraviolet source of 300-500nm, irradiation 10-30 solidifies second at wavelength.
The present embodiment effect: can obtain through electronic universal drawing machine and fluid density test conventional method: tensile strength is 13.88MPa, and elongation at break is 66%, and density is 1.27g/cm
3(25 DEG C).
Embodiment 7
A kind of containing macromole elastomeric 3D printed photosensitive resin material, composed as follows: mixed light initiator 3%; Methacrylic acid norbornene ester 10%; NVP 2%; Macromole elastomerics 30%; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 25%; Diethoxy dihydroxyphenyl propane two propylene 30%.
Wherein, the R in tertiary amine-type benzoate structure formula is butyl.
Above-mentioned one contains macromole elastomeric 3D printed photosensitive resin material, and its preparation method is as follows:
(1) the elastomeric preparation of macromole: with embodiment 1;
(2) methacrylic acid norbornene ester 10g is taken respectively; NVP 2g; Macromole elastomerics 30g; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 25g; Diethoxy dihydroxyphenyl propane two propylene 30g, at stirrer for mixing 1h, stirring velocity is 500r/min, light trigger 1173,369 and tertiary amine-type benzoic ether 0.6g, 0.6g, 1.8g is added respectively under light protected environment, be uniformly mixed, standing 15min is applied on sheet glass, and smearing thickness is 1-5 μm, is that under the ultraviolet source of 300-500nm, irradiation 10-30 solidifies second at wavelength.
The present embodiment effect: can obtain through electronic universal drawing machine and fluid density test conventional method: tensile strength is 11.35MPa, and elongation at break is 54%, and density is 0.83g/cm3 (25 DEG C).
Embodiment 8:
A kind of containing macromole elastomeric 3D printed photosensitive resin material, composed as follows: mixed light initiator 5%; Methacrylic acid norbornene ester 15%; NVP 6%; Macromole elastomerics 45%; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 15%; Diethoxy dihydroxyphenyl propane two propylene 14%.
Wherein, the R in tertiary amine-type benzoate structure formula is sec.-propyl.
Above-mentioned one contains macromole elastomeric 3D printed photosensitive resin material, and its preparation method is as follows:
(1) the elastomeric preparation of macromole: with embodiment 1;
(2) methacrylic acid norbornene ester 15g is taken respectively; NVP 6g; Macromole elastomerics 45g; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 15g; Diethoxy dihydroxyphenyl propane two propylene 14g, at stirrer for mixing 1h, stirring velocity is 500r/min, light trigger 1173,369 and tertiary amine-type benzoic ether 1g, 1g, 3g is added respectively under light protected environment, be uniformly mixed, standing 15min is applied on sheet glass, and smearing thickness is 1-5 μm, is that under the ultraviolet source of 300-500nm, irradiation 10-30 solidifies second at wavelength.
The present embodiment effect: can obtain through electronic universal drawing machine and fluid density test conventional method: tensile strength is 14.98MPa, and elongation at break is 82%, and density is 1.35g/cm
3(25 DEG C).
Embodiment 9:
A kind of containing macromole elastomeric 3D printed photosensitive resin material, composed as follows: mixed light initiator 3%; Methacrylic acid norbornene ester 14%; NVP 4%; Macromole elastomerics 33%; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 20%; Diethoxy dihydroxyphenyl propane two propylene 26%.
Wherein, the R in tertiary amine-type benzoate structure formula is propyl group.
Above-mentioned one contains macromole elastomeric 3D printed photosensitive resin material, and its preparation method is as follows:
(1) the elastomeric preparation of macromole: as embodiment 1;
(2) methacrylic acid norbornene ester 14g is taken respectively; NVP 4g; Macromole elastomerics 33g; Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether 20g; Diethoxy dihydroxyphenyl propane two propylene 26g, at stirrer for mixing 1h, stirring velocity is 500r/min, light trigger 1173,369 and tertiary amine-type benzoic ether 0.6g, 0.6g, 1.8g is added respectively under light protected environment, be uniformly mixed, standing 15min is applied on sheet glass, and smearing thickness is 1-5 μm, is that under the ultraviolet source of 300-500nm, irradiation 10-30 solidifies second at wavelength.
The present embodiment effect: can obtain through electronic universal drawing machine and fluid density test conventional method: tensile strength is 9.47MPa, and elongation at break is 51%, and density is 0.91g/cm3 (25 DEG C).
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (6)
1. one kind contains macromole elastomeric 3D printed photosensitive resin material, it is characterized in that: by mass percentage by component: mixed light initiator is 1-5%, methacrylic acid norbornene ester is 8-18%, NVP is 1-7%, macromole elastomerics is 30-50%, and Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether is 10-25%, diethoxy dihydroxyphenyl propane two propylene is 10-30% composition, and wherein said macromole elastomerics is single ethene macromonomer.
2. one according to claim 1 contains macromole elastomeric 3D printed photosensitive resin material, it is characterized in that: described mixed light initiator, be made up of light trigger 1173, light trigger 369 and tertiary amine-type benzoic ether, its ratio is light trigger 1173: light trigger 369: tertiary amine-type benzoic ether=1:1:3, and wherein the molecular structure of tertiary amine-type benzoic ether is:
Wherein, R group is the alkyl containing 1-7 carbon atom, comprises the isomers gone out by alkyl derivative.
3. one according to claim 1 contains macromole elastomeric 3D printed photosensitive resin material, it is characterized in that: described macromole elastomerics is single ethene macromonomer, namely with the phenyl lithium containing double bond for initiator, by anionoid polymerization isoprene, being formed with isoprene is that A block, oxyethane have an elastic polymer polymeric monomer of terminal ethylenic base for B block.
4. one according to claim 3 contains macromole elastomeric 3D printed photosensitive resin material, it is characterized in that: the molecular structure of the described phenyl lithium containing double bond is:
5. one according to claim 3 contains macromole elastomeric 3D printed photosensitive resin material, it is characterized in that: the molecular structure of described single ethene macromonomer is:
Wherein, n>m, n:m=1.5:1, n=15-45, m=10-30, its molecular weight is 1000-10000.
6. the preparation method containing macromole elastomeric 3D printed photosensitive resin material according to claim 1, is characterized in that comprising as 1 step:
(1) macromole elastomerics is prepared: according to the basic step of anionoid polymerization, take toluene as solvent, be sequentially added into containing lithium initiator and isoprene, at 90-100 DEG C of temperature, react 2h be down to room temperature, add oxyethane liquid, 50-70 DEG C of reaction 1h, is (4-8) containing the mass ratio of lithium initiator, isoprene, oxyethane at wherein said toluene: (0.5-1): 1:1;
(2) content takes each raw material of composition photosensitive resin material by mass percentage, and be placed on stirrer for mixing, with the rotating speed of 500r/min, mix and blend 1h, obtains photosensitive resin material;
(3) step (2) being obtained photosensitive resin material is applied on sheet glass, and smearing thickness is 1-5 μm, and under ultraviolet source, irradiation 10-30 solidifies second, and it is 300-500nm that photo solidification machine arranges wavelength.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510604989.1A CN105175645B (en) | 2015-09-21 | 2015-09-21 | A kind of 3D printing photosensitive resin material and preparation method containing macromolecular elastomer |
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| CN201510604989.1A CN105175645B (en) | 2015-09-21 | 2015-09-21 | A kind of 3D printing photosensitive resin material and preparation method containing macromolecular elastomer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754052A (en) * | 2016-03-02 | 2016-07-13 | 辽宁拜斯特复合材料有限公司 | Photocuring resin material for 3D printing as well as preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307694A (en) * | 1998-06-11 | 2001-08-08 | 陶氏化学公司 | Photocurable elastomeric compositions |
| JP2007140269A (en) * | 2005-11-21 | 2007-06-07 | Asahi Kasei Chemicals Corp | Photosensitive resin composition for flexographic printing |
| CN104559196A (en) * | 2014-12-29 | 2015-04-29 | 大连理工常熟研究院有限公司 | Colorless and transparent light-cured 3D printing material |
-
2015
- 2015-09-21 CN CN201510604989.1A patent/CN105175645B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307694A (en) * | 1998-06-11 | 2001-08-08 | 陶氏化学公司 | Photocurable elastomeric compositions |
| JP2007140269A (en) * | 2005-11-21 | 2007-06-07 | Asahi Kasei Chemicals Corp | Photosensitive resin composition for flexographic printing |
| CN104559196A (en) * | 2014-12-29 | 2015-04-29 | 大连理工常熟研究院有限公司 | Colorless and transparent light-cured 3D printing material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754052A (en) * | 2016-03-02 | 2016-07-13 | 辽宁拜斯特复合材料有限公司 | Photocuring resin material for 3D printing as well as preparation method and application thereof |
| CN105754052B (en) * | 2016-03-02 | 2018-01-23 | 辽宁拜斯特复合材料有限公司 | A kind of 3D printing photocurable resin material and its preparation method and application |
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