CN104250422A - Photosensitive resin used in 3D printing, and its preparation method - Google Patents
Photosensitive resin used in 3D printing, and its preparation method Download PDFInfo
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- CN104250422A CN104250422A CN201310259101.6A CN201310259101A CN104250422A CN 104250422 A CN104250422 A CN 104250422A CN 201310259101 A CN201310259101 A CN 201310259101A CN 104250422 A CN104250422 A CN 104250422A
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Abstract
The invention provides a photosensitive resin used in 3D printing, and its preparation method. The photosensitive resin is prepared by using 35-40 parts of acrylate, 35-40 parts of epoxy resin, 20-30 parts of a diluent, 0.1-5 parts of an antifoaming agent, 0.1-5 parts of a leveling agent, 1-10 parts of a cationic initiator and 1-10 parts of a free radical photopolymerization initiator. The photosensitive resin prepared in the invention has the characteristics of fast forming speed, small irritation, simple process, low cost and the like, and can be directly applied in 3D printing to make products with complex structures.
Description
Technical field
The present invention relates to 3D printing technique field, be specifically related to a kind of photosensitive resin for 3D printing and preparation method thereof.
Background technology
3D printer, also known as 3 D Printer, is a kind of new manufacture based on bing area method, and its ultimate principle is " Layered manufacturing successively adds ".Utilize the mode such as laser beam, hot melt nozzle successively to be piled up by the exotic materialss such as metal-powder, ceramic powder, plastics, cell tissue to cohere, final superposition is shaping, produces entity products.First moved left and right by powder-laying roller during work, evenly lay for the powder in powder cylinder on moulding cylinder, then on the first layer powder, this cross-sectional shape is sprayed by printhead according to the part model designed, then moulding cylinder moves down, print the second layer according to this step again, make the overall each cross section of part be piled up formation goods by interlayer superposition.About there is existing Two decades years in 3D printing technique, but real large-scale fund and Technical investment from recent years just, the current U.S. has appropriated funds 1,000,000,000 dollars to set up national 3D and has printed additive industrial research center, and machine industry association of China manufactures first to determine 3D printer to arrange into China is following.
It is 17.14 hundred million dollars that global 3D in 2011 prints sales volume, increases by 29% on a year-on-year basis.The equipment that wherein product is directly used in batch production accounts for 19.2%, and batch application has promoted the surge of consumptive material kind and quantity undoubtedly on a large scale.The popularity that domestic 3D prints is lower, about the report of its special photosensitive resin material rarely has especially, photosensitive resin is made up of polymer monomer and performed polymer, wherein be added with light trigger (or being called photosensitizers), under the UV-light (250-300 nanometer) of certain wavelength is irradiated, cause polyreaction to complete solidification at once.Existing photosensitive resin causes that curing efficiency is low, part performance is poor, pungency is large and high in cost of production is not enough due to matrix collocation and the reason such as formulating of recipe.
Summary of the invention
The object of the present invention is to provide a kind of photosensitive resin for 3D printing and preparation method thereof.Photosensitive resin prepared by the present invention has that shaping speed is fast, pungency is little, technique is simple and the feature such as with low cost, can directly apply to 3D and print obtained baroque product.
For achieving the above object, the present invention is by the following technical solutions:
A kind of photosensitive resin for 3D printing and preparation method thereof, is prepared from by weight by following component:
Acrylate 35 ~ 40 parts,
Epoxy resin 35 ~ 40 parts,
Thinner 20 ~ 30 parts,
Defoamer 0.1 ~ 5 part,
Flow agent 0.1 ~ 5 part,
Cationic initiators 1 ~ 10 part,
Free radical type Photoepolymerizationinitiater initiater 1 ~ 10 part.
Described acrylate is at least one in epoxy monoacrylate, urethane acrylate and polyester acrylate.
Described epoxy resin is at least one in phenol aldehyde type, bisphenol A-type and Zhi Huan race epoxy resin.
Described thinner is at least one in glycidyl methacrylate, Viscoat 295, ethoxyquin base Viscoat 295, ethylene glycol diglycidylether and tripropyleneglycol diglycidyl ether.
Described defoamer is at least one in dimethyl polysiloxane, ethylene oxide propylene oxide copolyether and polyether silicone.
Described flow agent is at least one in organosilicon-epoxide ethane multipolymer, organosilicon-epoxide propane multipolymer and polydimethylsiloxane.
Described cationic initiators is salt compounded of iodine or sulfonium salt.
Described free radical type Photoepolymerizationinitiater initiater is at least one in benzophenone, diphenyl antimony chloride ketone and dimethoxybenzoin.
Another object of the present invention is to provide a kind of method preparing the above-mentioned photosensitive resin for 3D printing, comprises the following steps:
(1) in the special glass there-necked flask that agitator and prolong are housed, acrylate, epoxy resin, thinner, defoamer, flow agent, cationic initiators and free radical type Photoepolymerizationinitiater initiater is added successively;
(2) mixed solution in (1) is warming up to 50 DEG C ~ 80 DEG C, carries out stir about 15min ~ 30min with agitator, obtain faint yellow homogeneous liquid, be the photosensitive resin printed for 3D.
Beneficial effect of the present invention has:
1, owing to adding environment-friendly type thinner, the photosensitive resin of preparation does not have pungency, to environment and harm relatively little.
2, due to effective collocation of initiator and unsaturated polyester, significantly improve photosensitive resin shaping speed.
3, photosensitive resin of the present invention can directly apply to 3D and print obtained baroque product product, the photosensitive resin shaping speed prepared due to the present invention is fast, product product design and 3D can be realized print to produce and synchronously carry out, significantly improve Corporation R & D efficiency, shorten the product design cycle, reduce the cost and risk of exploitation.
4, consumptive material price needed for current SLS technology is at 250 ~ 460 dollars/kg, owing to adopting low cost unsaturated polyester in the present invention, the more existing consumptive material of the cost of final photosensitive resin is compared and significantly cuts down 50% ~ 70% cost, be conducive to the popularization and application work of batch production and 3D printing technique.
specific implementation method
Below in conjunction with specific examples, content of the present invention is further detailed; but described embodiment is not the simple restriction to connotation of the present invention, anyly all should to belong within the present invention's scope required for protection based on the simple change done by connotation of the present invention or equivalent replacement.
In specific embodiments of the invention if no special instructions, described in each embodiment, number is weight part.
embodiment 1
(1) raw material is equipped with in following ratio:
Epoxy monoacrylate 20 parts,
Urethane acrylate 15 parts,
Phenol aldehyde type epoxy resin 35 parts,
Glycidyl methacrylate 10 parts,
Viscoat 295 10 parts,
Defoamer dimethyl polysiloxane 0.1 part,
Flow agent organosilicon-epoxide ethane multipolymer 0.1 part,
Cationic initiators salt compounded of iodine 1 part,
Free radical type Photoepolymerizationinitiater initiater benzophenone 1 part,
Free radical type Photoepolymerizationinitiater initiater diphenyl antimony chloride ketone 1 part.
(2) in the special glass there-necked flask that agitator and prolong are housed, add above-mentioned raw materials successively to mix;
(3) mixed solution is warming up to 50 DEG C, carries out stir about 30min with agitator, obtain faint yellow homogeneous liquid, be the photosensitive resin printed for 3D.
embodiment 2
(1) raw material is equipped with in following ratio:
Epoxy monoacrylate 40 parts,
Phenol aldehyde type epoxy resin 15 parts,
Bisphenol A type epoxy resin 20 parts,
Glycidyl methacrylate 10 parts,
Ethoxyquin base Viscoat 295 15 parts,
Defoamer dimethyl polysiloxane 1 part,
Defoamer polyether silicone 1 part,
Flow agent organosilicon-epoxide ethane copolymer 1 part,
Flow agent organosilicon-epoxide propane copolymer 1 part,
Cationic initiators salt compounded of iodine 1 part,
Free radical type Photoepolymerizationinitiater initiater benzophenone 3 parts.
(2) in the special glass there-necked flask that agitator and prolong are housed, add above-mentioned raw materials successively to mix;
(3) mixed solution is warming up to 60 DEG C, carries out stir about 25min with agitator, obtain faint yellow homogeneous liquid, be the photosensitive resin printed for 3D.
embodiment 3
(1) raw material is equipped with in following ratio:
Epoxy monoacrylate 35 parts,
Phenol aldehyde type epoxy resin 40 parts,
Viscoat 295 20 parts,
Defoamer dimethyl polysiloxane 2 parts,
Flow agent organosilicon-epoxide ethane multipolymer 2 parts,
Cationic initiators salt compounded of iodine 5 parts,
Free radical type Photoepolymerizationinitiater initiater benzophenone 8 parts.
(2) in the special glass there-necked flask that agitator and prolong are housed, add above-mentioned raw materials successively to mix;
(3) mixed solution is warming up to 70 DEG C, carries out stir about 20min with agitator, obtain faint yellow homogeneous liquid, be the photosensitive resin printed for 3D.
embodiment 4
(1) raw material is equipped with in following ratio:
Epoxy monoacrylate 40 parts,
Phenol aldehyde type epoxy resin 35 parts,
Viscoat 295 25 parts,
Defoamer dimethyl polysiloxane 5 parts,
Flow agent organosilicon-epoxide ethane multipolymer 5 parts,
Cationic initiators salt compounded of iodine 5 parts,
Free radical type Photoepolymerizationinitiater initiater benzophenone 10 parts.
(2) in the special glass there-necked flask that agitator and prolong are housed, add above-mentioned raw materials successively to mix;
(3) mixed solution is warming up to 80 DEG C, carries out stir about 15min with agitator, obtain faint yellow homogeneous liquid, be the photosensitive resin printed for 3D.
embodiment 5
(1) raw material is equipped with in following ratio:
Urethane acrylate 35 parts,
Bisphenol A type epoxy resin 38 parts,
Ethoxyquin base Viscoat 295 25 parts,
Defoamer dimethyl polysiloxane 4 parts,
Flow agent organosilicon-epoxide ethane multipolymer 5 parts,
Cationic initiators salt compounded of iodine 10 parts,
Free radical type Photoepolymerizationinitiater initiater diphenyl antimony chloride ketone 1 part.
(2) in the special glass there-necked flask that agitator and prolong are housed, add above-mentioned raw materials successively to mix;
(3) mixed solution is warming up to 50 DEG C, carries out stir about 30min with agitator, obtain faint yellow homogeneous liquid, be the photosensitive resin printed for 3D.
embodiment 6
(1) raw material is equipped with in following ratio:
Urethane acrylate 38 parts,
Bisphenol A type epoxy resin 35 parts,
Ethoxyquin base Viscoat 295 25 parts,
Defoamer ethylene oxide propylene oxide copolyether 1 part,
Flow agent organosilicon-epoxide propane copolymer 1 part,
Cationic initiators salt compounded of iodine 10 parts,
Free radical type Photoepolymerizationinitiater initiater diphenyl antimony chloride ketone 3 parts.
(2) in the special glass there-necked flask that agitator and prolong are housed, add above-mentioned raw materials successively to mix;
(3) mixed solution is warming up to 50 DEG C, carries out stir about 30min with agitator, obtain faint yellow homogeneous liquid, be the photosensitive resin printed for 3D.
embodiment 7
(1) raw material is equipped with in following ratio:
Urethane acrylate 37 parts,
Bisphenol A type epoxy resin 38 parts,
Ethylene glycol diglycidylether 25 parts,
Defoamer ethylene oxide propylene oxide copolyether 2 parts,
Flow agent organosilicon-epoxide propane multipolymer 2 parts,
Cationic initiators sulfonium salt 1 part,
Free radical type Photoepolymerizationinitiater initiater diphenyl antimony chloride ketone 8 parts.
(2) in the special glass there-necked flask that agitator and prolong are housed, add above-mentioned raw materials successively to mix;
(3) mixed solution is warming up to 50 DEG C, carries out stir about 30min with agitator, obtain faint yellow homogeneous liquid, be the photosensitive resin printed for 3D.
embodiment 8
(1) raw material is equipped with in following ratio:
Urethane acrylate 38 parts,
Bisphenol A type epoxy resin 37 parts,
Ethylene glycol diglycidylether 25 parts,
Defoamer ethylene oxide propylene oxide copolyether 5 parts,
Flow agent organosilicon-epoxide propane multipolymer 5 parts,
Cationic initiators sulfonium salt 1 part,
Free radical type Photoepolymerizationinitiater initiater diphenyl antimony chloride ketone 10 parts.
(2) in the special glass there-necked flask that agitator and prolong are housed, add above-mentioned raw materials successively to mix;
(3) mixed solution is warming up to 50 DEG C, carries out stir about 30min with agitator, obtain faint yellow homogeneous liquid, be the photosensitive resin printed for 3D.
embodiment 9
(1) raw material is equipped with in following ratio:
Polyester acrylate 38 parts,
Zhi Huan race epoxy resin 40 parts,
Tripropyleneglycol diglycidyl ether 30 parts,
Defoamer polyether silicone 3 parts,
Flow agent polydimethylsiloxane 5 parts,
Cationic initiators sulfonium salt 5 parts,
Free radical type Photoepolymerizationinitiater initiater dimethoxybenzoin 1 part.
(2) in the special glass there-necked flask that agitator and prolong are housed, add above-mentioned raw materials successively to mix;
(3) mixed solution is warming up to 50 DEG C, carries out stir about 30min with agitator, obtain faint yellow homogeneous liquid, be the photosensitive resin printed for 3D.
embodiment 10
(1) raw material is equipped with in following ratio:
Polyester acrylate 40 parts,
Zhi Huan race epoxy resin 38 parts,
Tripropyleneglycol diglycidyl ether 30 parts,
Defoamer polyether silicone 1 part,
Flow agent polydimethylsiloxane 1 part,
Cationic initiators sulfonium salt 5 parts,
Free radical type Photoepolymerizationinitiater initiater dimethoxybenzoin 3 parts.
(2) in the special glass there-necked flask that agitator and prolong are housed, add above-mentioned raw materials successively to mix;
(3) mixed solution is warming up to 50 DEG C, carries out stir about 30min with agitator, obtain faint yellow homogeneous liquid, be the photosensitive resin printed for 3D.
embodiment 11
(1) raw material is equipped with in following ratio:
Polyester acrylate 40 parts,
Zhi Huan race epoxy resin 35 parts,
Glycidyl methacrylate 30 parts,
Defoamer polyether silicone 2 parts,
Flow agent polydimethylsiloxane 2 parts,
Cationic initiators sulfonium salt 10 parts,
Free radical type Photoepolymerizationinitiater initiater dimethoxybenzoin 8 parts.
(2) in the special glass there-necked flask that agitator and prolong are housed, add above-mentioned raw materials successively to mix;
(3) mixed solution is warming up to 50 DEG C, carries out stir about 30min with agitator, obtain faint yellow homogeneous liquid, be the photosensitive resin printed for 3D.
embodiment 12
(1) raw material is equipped with in following ratio:
Polyester acrylate 35 parts,
Zhi Huan race epoxy resin 40 parts,
Glycidyl methacrylate 30 parts,
Defoamer polyether silicone 5 parts,
Flow agent polydimethylsiloxane 5 parts,
Cationic initiators sulfonium salt 10 parts,
Free radical type Photoepolymerizationinitiater initiater dimethoxybenzoin 10 parts.
(2) in the special glass there-necked flask that agitator and prolong are housed, add above-mentioned raw materials successively to mix;
(3) mixed solution is warming up to 50 DEG C, carries out stir about 30min with agitator, obtain faint yellow homogeneous liquid, be the photosensitive resin printed for 3D.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (9)
1., for the photosensitive resin that 3D prints, it is characterized in that: be prepared from by weight by following component:
Acrylate 35 ~ 40 parts,
Epoxy resin 35 ~ 40 parts,
Thinner 20 ~ 30 parts,
Defoamer 0.1 ~ 5 part,
Flow agent 0.1 ~ 5 part,
Cationic initiators 1 ~ 10 part,
Free radical type Photoepolymerizationinitiater initiater 1 ~ 10 part.
2. a kind of photosensitive resin printed for 3D according to claim 1, is characterized in that: described acrylate is at least one in epoxy monoacrylate, urethane acrylate and polyester acrylate.
3. a kind of photosensitive resin printed for 3D according to claim 1, it is characterized in that, described epoxy resin is at least one in phenol aldehyde type, bisphenol A-type and Zhi Huan race epoxy resin.
4. a kind of photosensitive resin printed for 3D according to claim 1, is characterized in that: described thinner is at least one in glycidyl methacrylate, Viscoat 295, ethoxyquin base Viscoat 295, ethylene glycol diglycidylether and tripropyleneglycol diglycidyl ether.
5. a kind of photosensitive resin printed for 3D according to claim 1, is characterized in that: described defoamer is at least one in dimethyl polysiloxane, ethylene oxide propylene oxide copolyether and polyether silicone.
6. a kind of photosensitive resin printed for 3D according to claim 1, is characterized in that: described flow agent is preferably at least one in organosilicon-epoxide ethane multipolymer, organosilicon-epoxide propane multipolymer and polydimethylsiloxane.
7. a kind of photosensitive resin printed for 3D according to claim 1, is characterized in that: described cationic initiators is salt compounded of iodine or sulfonium salt.
8. a kind of photosensitive resin printed for 3D according to claim 1, is characterized in that: described free radical type Photoepolymerizationinitiater initiater is at least one in benzophenone, diphenyl antimony chloride ketone and dimethoxybenzoin.
9. prepare a method for the photosensitive resin printed for 3D as claimed in claim 1, it is characterized in that: comprise the following steps:
(1) in the glass there-necked flask that agitator and prolong are housed, acrylate, epoxy resin, thinner, defoamer, flow agent, cationic initiators and free radical type Photoepolymerizationinitiater initiater is added successively by proportioning;
(2) mixed solution in (1) is warming up to 50 DEG C ~ 80 DEG C, carries out stir about 15min ~ 30min with agitator, obtain faint yellow homogeneous liquid, be the photosensitive resin printed for 3D.
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| CN104893224A (en) * | 2015-06-23 | 2015-09-09 | 广东博兴新材料科技有限公司 | Application of low-viscosity light-cured resin in 3D (three-dimensional) printing materials |
| CN105116686A (en) * | 2015-08-28 | 2015-12-02 | 江门市恒光新材料有限公司 | Photosensitive resin for 3D printing |
| CN105399908A (en) * | 2015-12-23 | 2016-03-16 | 河南工程学院 | New UV laser curing rapid molding photosensitive resin and preparation method thereof |
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