CN105399905A - Light-cured three dimensional printing material and preparation method thereof - Google Patents
Light-cured three dimensional printing material and preparation method thereof Download PDFInfo
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- CN105399905A CN105399905A CN201510706463.4A CN201510706463A CN105399905A CN 105399905 A CN105399905 A CN 105399905A CN 201510706463 A CN201510706463 A CN 201510706463A CN 105399905 A CN105399905 A CN 105399905A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
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Abstract
The invention discloses a light-cured three dimensional printing material and a preparation method thereof. The light-cured three dimensional printing material comprises, by mass, 40-45 parts of polyester modified epoxy acrylate, 8-12 parts of cycloaliphatic epoxy resin, 8-10 parts of trihydroxymethylpropyl trimethylacrylate, 16-20 parts of 1,6-hexanediol diacrylate, 2-8 parts of triethyleneglycol divinyl ether, 1.5-2 parts of isopropylthioxanthone, 1.5-2 parts of 2-phenyl-2,2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 1.5-2 parts of a reactive tertiary amine co-initiator, 0.5-2.7 parts of 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate, 0.5-2 parts of an anthraquinone derivative, 0.5-2 parts of a promoter and 4-8 parts of a flexibilizer. Shaped parts made by using the light-cured three dimensional printing material have the advantages of low shrinkage, high toughness and high shaping precision.
Description
Technical field
The invention belongs to field of polymer composite material, particularly a kind of photocuring 3 D-printing material and preparation method thereof.
Background technology
Photocuring 3 D-printing is also referred to as quantitation manufacture or increases material manufacture, is according to droplet ejection principle, is ejected on work top by printed material, then be cured by UV-light and a kind of technique of successively piling up.Three Dimensional Printing of Rapid Prototyping technology, has traditional machining and the incomparable advantage of forced shaping, since the nineties in 20th century, the people such as Massachusetts Institute Technology EmanualSachs proposed first, has attracted numerous scholar to participate in research.Printer in the market and printed material mostly are external imported product, expensive, its resin used is generally by the development of strong major company, exploitation, production, and technical know-how, although the 3 D-printing equipment of domestic existing unit research and development relative low price and resin, the improvement but its precision and reliability are still needed, and light-cured resin kind is single, greatly limit popularization and the use of three-dimensional printing technology.
The major ingredient of photocuring 3 D-printing material is epoxy resin and acrylate thereof, and its cured product has the three-dimensional reticulated structure body compared with high crosslink density, the motion of main chain is very difficult, thus the shock strength of photocuring three-dimensional printing-forming part is lower, snappiness is poor, adds its cured product and can cause cracking because of deformation, stress concentration when cold and hot temperature sharply changes.In view of the purposes of photocuring three-dimensional printing-forming part is more and more extensive, present trend is the application of deflection functional part, and meaning and drip molding are directly used as part, and this just requires that photocuring 3 D-printing material has good toughness, shock resistance.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the object of this invention is to provide a kind of good toughness, photocuring 3 D-printing material that shock strength is high and preparation method thereof, to improve the intensity of profiled member, toughness and forming accuracy.
For achieving the above object, the present invention is by the following technical solutions:
A kind of photocuring 3 D-printing material, in mass fraction, its raw material is composed of the following components:
Described promotor is polyol C
3h
4oH (COOH)
3, its role is to the ring-opening reaction that can promote epoxy group(ing), significantly improve solidification rate and crosslinking degree, make cured article top layer and bottom synchronous reaction, be issued to fast setting at thick film and Low emissivity energy condition.
Described toughner is fluid rubber epoxidation hydroxy-terminated polybutadienes EHTPB, molecular weight is 3000 ~ 3600, it introduces epoxide group on the hydroxy-terminated polybutadienes segment of flexibility, and cause with positively charged ion and free radical initiation polymerization participation simultaneously photocuring reaction, with resin formation inierpeneirating network structure, thus improve the toughness of resin matrix.
A preparation method for photocuring 3 D-printing material, comprises the steps:
A) by thinner 1,6-hexanediyl ester, trimethylolpropane trimethacrylate and triethyleneglycol divinylether, light trigger 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, isopropyl thioxanthone, response type tertiary amine aided initiating, 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate and sensitizing agent anthraquinone derivative and promotor polyol add in container and stir 2 hours in heat-collecting magnetic stirring device;
B) by prepolymer polyester modified epoxy acrylic ester and cycloaliphatic epoxy resin, toughner epoxidation hydroxy-terminated polybutadienes adds in the middle of the mixed solution that above-mentioned steps A prepares, be heated to 50 DEG C again with the rotating speed magnetic agitation 1-2h of 600-700rpm, prepare the photocuring 3 D-printing material of yellow transparent.
Beneficial effect of the present invention is:
(1) double bond on epoxidation hydroxyl terminated polybutadiene rubber molecular chain and epoxy-functional have certain activity, can cause under free radical and cationic existence and carry out further crosslinking reaction, form inierpeneirating network structure (IPN) with printed material.To be that a kind of material is random extend through in another kind of material the feature of inierpeneirating network structure, makes to create synergistic effect between two components in interpenetrating network system, thus make cured product obtain more excellent performance.
(2) the present invention adopts free radical-positively charged ion to combine curing system, when intending utilizing cationic performed polymer ring-opening polymerization, volumetric expansion reaches the object reducing and shrink, the photocuring 3 D-printing profiled member forming accuracy of preparation is greatly improved, is more widely used in the manufacture field of multiple high strength such as industry manufacture, die design, high-precision part.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described.
Embodiment 1
1, in mass parts, raw material is prepared according to table 1 Suo Shi.
The each proportioning raw materials of table 1 embodiment 1
| Raw material | Embodiment 1 |
| Polyester modification epoxy acrylate | 40 parts |
| Aliphatic epoxy resin | 12 parts |
| Trimethylolpropane trimethacrylate | 8 parts |
| 1,6 hexanediol diacrylate | 20 parts |
| Triethyleneglycol divinylether | 2 parts |
| Isopropyl thioxanthone | 2 parts |
| 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone | 1.5 part |
| Response type tertiary amine aided initiating 6420 | 2 parts |
| 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate | 1.5 part |
| Sensitizing agent anthraquinone derivative PAS-12 | 2 parts |
| Promotor polyol PAS-33 | 1 part |
| Toughner epoxidation hydroxy-terminated polybutadienes EHTPB | 8 parts |
1.1 preparation methods:
A) in mass parts, by thinner 1.6-hexanediyl ester 20 parts, trimethylolpropane trimethacrylate 8 parts and triethyleneglycol divinylether 2 parts, light trigger isopropyl thioxanthone 2 parts, 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone 1.5 parts, response type tertiary amine aided initiating 2 parts and 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate 1.5 parts and sensitizing agent anthraquinone derivative 2 parts and promotor polyol 1 part add in beaker and stir 2 hours in heat-collecting magnetic stirring device.
B) in mass parts, prepolymer polyester modified epoxy acrylic ester 40 parts, cycloaliphatic epoxy resin 12 parts and toughner epoxidation hydroxy-terminated polybutadienes 8 parts are added in the middle of mixed solution that above-mentioned steps A prepares, be heated to 50 DEG C with the rotating speed magnetic agitation 1-2h of 600-700rpm, prepare the photocuring 3 D-printing material of yellow transparent.
1.2 molding parameters are:
Uv cure machine high voltage mercury lamp power 2000W, emission wavelength 365nm and 385nm, sweep velocity 17.36m/min, irradiation distance 8mm, solidification thickness 0.1mm, solidification value is room temperature, with sheet glass and cured resin successively pile up shaping for substrate.
1.3 detected results:
The photocuring 3 D-printing materials application that embodiment 1 is obtained in 3 D-printing shaping and to solidification after material carry out Performance Detection, detected result is as shown in table 2.
Table 2 embodiment 1 material property detected result
| Test item | Embodiment 1 |
| Viscosity (25 DEG C) | 254.6mPa·s |
| Density (25 DEG C) before solidification | 1.1023g/cm 3 |
| Surface tension | 30.5mN/m |
| Curing speed | 17.36m/min |
| Density (25 DEG C) after solidification | 1.1550g/cm 3 |
| Threshold exposure amount | 9.2mJ/cm 2 |
| Transmission depth | 0.20mm |
| Degree of cure | 98.64％ |
| Volumetric shrinkage | 4.56％ |
| Hardness | 76.1HD |
| Tensile strength | 22.35MPa |
| Modulus in flexure | 772.95MPa |
| Elongation at break | 6.8％ |
| Flexural strength | 24.39MPa |
| Shock strength | 10.34KJ/m 2 |
Embodiment 2
2., in mass parts, prepare raw material according to table 3 Suo Shi respectively
The each proportioning raw materials of table 3 embodiment 2
| Raw material | Embodiment 2 |
| Polyester modification epoxy acrylate | 43.5 parts |
| Aliphatic epoxy resin | 9 parts |
| Trimethylolpropane trimethacrylate | 9 parts |
| 1,6 hexanediol diacrylate | 18 parts |
| Triethyleneglycol divinylether | 5 parts |
| Isopropyl thioxanthone | 1.5 part |
| 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone | 2 parts |
| Response type tertiary amine aided initiating | 1.7 part |
| 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate | 0.5 part |
| Sensitizing agent anthraquinone derivative PAS-12 | 1.8 part |
| Promotor polyol PAS-33 | 2 parts |
| Toughner epoxidation hydroxy-terminated polybutadienes EHTPB | 6 parts |
2.1 preparation methods:
A) in mass parts, by thinner 1,6-hexanediyl ester 18 parts, trimethylolpropane trimethacrylate 9 parts and triethyleneglycol divinylether 5 parts, light trigger isopropyl thioxanthone 1.5 parts, 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone 2 parts and 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate 0.5 part, response type tertiary amine aided initiating 1.7 parts and sensitizing agent anthraquinone derivative 1.8 parts and promotor polyol 2 parts add in beaker and stir 2 hours in heat-collecting magnetic stirring device.
B) in mass parts, prepolymer polyester modified epoxy acrylic ester 43.5 parts, cycloaliphatic epoxy resin 9 parts and toughner epoxidation hydroxy-terminated polybutadienes 6 parts are added in the middle of mixed solution that above-mentioned steps A prepares, be heated to 50 DEG C with the rotating speed magnetic agitation 1-2h of 600-700rpm, prepare the photocuring 3 D-printing material of yellow transparent.
2.2 molding parameters are:
Uv cure machine high voltage mercury lamp power 2000W, emission wavelength 365nm and 385nm, sweep velocity 17.06m/min, irradiation distance 8mm, solidification thickness 0.1mm, solidification value is room temperature, with sheet glass and cured resin successively pile up shaping for substrate.
2.3 detected results:
The photocuring 3 D-printing materials application that embodiment 2 is obtained in 3 D-printing shaping and to solidification after material carry out Performance Detection, detected result is as shown in table 4.
Table 4 embodiment 2 material property detected result
| Test item | Embodiment 2 |
| Viscosity (25 DEG C) | 268.2mPa·s |
| Density (25 DEG C) before solidification | 1.1046g/cm 3 |
| Surface tension | 31.4mN/m |
| Curing speed | 17.06m/min |
| Density (25 DEG C) after solidification | 1.1539g/cm 3 |
| Threshold exposure amount | 8.9mJ/cm 2 |
| Transmission depth | 0.17mm |
| Degree of cure | 98.23％ |
| Volumetric shrinkage | 4.27％ |
| Hardness | 76.4HD |
| Tensile strength | 21.82MPa |
| Modulus in flexure | 771.60MPa |
| Elongation at break | 10.2％ |
| Flexural strength | 24.67MPa |
| Shock strength | 11.91KJ/m 2 |
Embodiment 3
3., in mass parts, prepare raw material according to table 5 Suo Shi respectively
The each proportioning raw materials of table 5 embodiment 3
| Raw material | Embodiment 3 |
| Polyester modification epoxy acrylate | 45 parts |
| Aliphatic epoxy resin | 8 parts |
| Trimethylolpropane trimethacrylate | 10 parts |
| 1,6 hexanediol diacrylate | 16 parts |
| Triethyleneglycol divinylether | 8 parts |
| Isopropyl thioxanthone | 1.9 part |
| 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone | 1.9 part |
| Response type tertiary amine aided initiating | 1.5 part |
| 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate | 2.7 part |
| Sensitizing agent anthraquinone derivative PAS-12 | 0.5 part |
| Promotor polyol PAS-33 | 0.5 part |
| Toughner epoxidation hydroxy-terminated polybutadienes EHTPB | 4 parts |
3.1 preparation methods:
A) in mass parts, by thinner 1,6-hexanediyl ester 16 parts, trimethylolpropane trimethacrylate 10 parts and triethyleneglycol divinylether 8 parts, light trigger isopropyl thioxanthone 1.9 parts, 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone 1.9 parts and 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate 2.7 parts, response type tertiary amine aided initiating 1.5 parts and sensitizing agent anthraquinone derivative 0.5 part and promotor polyol 0.5 part add in beaker and stir 2 hours in heat-collecting magnetic stirring device.
B) in mass parts, prepolymer polyester modified epoxy acrylic ester 45 parts, cycloaliphatic epoxy resin 8 parts and toughner epoxidation hydroxy-terminated polybutadienes 4 parts are added in the middle of solution that above-mentioned steps A prepares, be heated to 50 DEG C with the rotating speed magnetic agitation 1-2h of 600-700rpm, prepare the photocuring 3 D-printing material of yellow transparent.
3.2 molding parameters are:
Uv cure machine high voltage mercury lamp power 2000W, emission wavelength 365nm and 385nm, sweep velocity 16.49m/min, irradiation distance 8mm, solidification thickness 0.1mm, solidification value is room temperature, with sheet glass and cured resin successively pile up shaping for substrate.
3, detected result:
The photocuring 3 D-printing materials application that embodiment 3 is obtained in 3 D-printing shaping and to solidification after material carry out Performance Detection, detected result is as shown in table 6.
Table 6 embodiment 3 material property detected result
| Test item | Embodiment 3 |
| Viscosity (25 DEG C) | 279.8mPa·s |
| Density (25 DEG C) before solidification | 1.1091g/cm 3 |
| Surface tension | 32.2mN/m |
| Curing speed | 16.49m/min |
| Density (25 DEG C) after solidification | 1.1917g/cm 3 |
| Threshold exposure amount | 8.2mJ/cm 2 |
| Transmission depth | 0.13mm |
| Degree of cure | 97.26％ |
| Volumetric shrinkage | 6.93％ |
| Hardness | 78.5HD |
| Tensile strength | 20.46MPa |
| Modulus in flexure | 724.74MPa |
| Elongation at break | 7.4％ |
| Flexural strength | 23.19MPa |
| Shock strength | 11.06KJ/m 2 |
In above-described embodiment 1-3, polyester modification epoxy acrylate HS9103 is that a chemical material company limited is added in Guangzhou; Cycloaliphatic epoxy resin UVR-6128 is provided by Hubei Xinjing New Material Co., Ltd..
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 (4)
1. a photocuring 3 D-printing material, is characterized in that: in mass fraction, and its raw material is composed of the following components:
2. photocuring 3 D-printing material according to claim 1, is characterized in that: described promotor is polyol C
3h
4oH (COOH)
3.
3. photocuring 3 D-printing material according to claim 1, is characterized in that: described toughner is fluid rubber epoxidation hydroxy-terminated polybutadienes, and molecular weight is 3000 ~ 3600.
4. a preparation method for the photocuring 3 D-printing material as described in as arbitrary in claim 1-3, is characterized in that: comprise the steps:
A) by thinner 1,6-hexanediyl ester, trimethylolpropane trimethacrylate and triethyleneglycol divinylether, light trigger 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, isopropyl thioxanthone, response type tertiary amine aided initiating, 4-isobutyl phenenyl-4 '-aminomethyl phenyl iodine hexafluorophosphate and sensitizing agent anthraquinone derivative and promotor polyol add in container and stir 2 hours in heat-collecting magnetic stirring device;
B) by prepolymer polyester modified epoxy acrylic ester and cycloaliphatic epoxy resin, toughner epoxidation hydroxy-terminated polybutadienes adds in the middle of the mixed solution that above-mentioned steps A prepares, be heated to 50 DEG C again with the rotating speed magnetic agitation 1-2h of 600-700rpm, prepare the photocuring 3 D-printing material of yellow transparent.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106543705A (en) * | 2016-10-24 | 2017-03-29 | 上海臣光工业介质有限公司 | A kind of low temperature resistant photocuring 3D printing material and preparation method thereof |
| CN106647167A (en) * | 2016-09-30 | 2017-05-10 | 河南工程学院 | Matte photosensitive resin for photocuring quick molding and preparation method thereof |
| CN106751349A (en) * | 2016-12-12 | 2017-05-31 | 中山大简高分子材料有限公司 | A kind of radical cation hybrid UV-curing resin and preparation method and application |
| CN106749986A (en) * | 2016-12-12 | 2017-05-31 | 中山大简高分子材料有限公司 | A kind of epoxy phenolic resin composition for photocuring rapid prototyping |
| CN106832149A (en) * | 2017-01-11 | 2017-06-13 | 杭州龙勤新材料科技有限公司 | A kind of easy to be release photosensitive resin for 3D printing and preparation method thereof |
| CN107300828A (en) * | 2016-04-15 | 2017-10-27 | 常州强力电子新材料股份有限公司 | A kind of photosensitive resin for 3D printing |
| CN107722193A (en) * | 2017-10-18 | 2018-02-23 | 中山大简科技有限公司 | A kind of high rigidity photosensitive resin composition for photocuring rapid prototyping |
| CN109206566A (en) * | 2017-07-04 | 2019-01-15 | 北京橡胶工业研究设计院 | A kind of 3D printing photo-curing material and preparation method thereof containing Heveatex |
| CN109777023A (en) * | 2018-12-20 | 2019-05-21 | 宁波浙创科技有限公司 | A kind of 3D printing SLA flexible photosensitive resin and preparation method thereof |
| CN109777024A (en) * | 2019-01-08 | 2019-05-21 | 宁波浙创科技有限公司 | A kind of 3D printing SLA elasticity photosensitive resin and preparation method thereof |
| CN111377738A (en) * | 2020-02-11 | 2020-07-07 | 甘肃机电职业技术学院（甘肃省机械工业学校、甘肃省机械高级技工学校） | Preparation method of ceramic material for 3d printing |
| CN114634613A (en) * | 2022-03-21 | 2022-06-17 | 北京印刷学院 | Color 3D printing material and application thereof |
| CN115124879A (en) * | 2022-05-30 | 2022-09-30 | 无锡市科虹标牌有限公司 | Production method of LED display lamp source softening diffusion diaphragm |
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| CN106647167A (en) * | 2016-09-30 | 2017-05-10 | 河南工程学院 | Matte photosensitive resin for photocuring quick molding and preparation method thereof |
| CN106543705A (en) * | 2016-10-24 | 2017-03-29 | 上海臣光工业介质有限公司 | A kind of low temperature resistant photocuring 3D printing material and preparation method thereof |
| CN106751349A (en) * | 2016-12-12 | 2017-05-31 | 中山大简高分子材料有限公司 | A kind of radical cation hybrid UV-curing resin and preparation method and application |
| CN106749986A (en) * | 2016-12-12 | 2017-05-31 | 中山大简高分子材料有限公司 | A kind of epoxy phenolic resin composition for photocuring rapid prototyping |
| CN106832149B (en) * | 2017-01-11 | 2019-01-08 | 杭州龙勤新材料科技有限公司 | A kind of easy release photosensitive resin and preparation method thereof for 3D printing |
| CN106832149A (en) * | 2017-01-11 | 2017-06-13 | 杭州龙勤新材料科技有限公司 | A kind of easy to be release photosensitive resin for 3D printing and preparation method thereof |
| CN109206566A (en) * | 2017-07-04 | 2019-01-15 | 北京橡胶工业研究设计院 | A kind of 3D printing photo-curing material and preparation method thereof containing Heveatex |
| CN107722193A (en) * | 2017-10-18 | 2018-02-23 | 中山大简科技有限公司 | A kind of high rigidity photosensitive resin composition for photocuring rapid prototyping |
| CN109777023A (en) * | 2018-12-20 | 2019-05-21 | 宁波浙创科技有限公司 | A kind of 3D printing SLA flexible photosensitive resin and preparation method thereof |
| CN109777023B (en) * | 2018-12-20 | 2021-09-17 | 宁波浙创科技有限公司 | SLA flexible photosensitive resin for 3D printing and preparation method thereof |
| CN109777024A (en) * | 2019-01-08 | 2019-05-21 | 宁波浙创科技有限公司 | A kind of 3D printing SLA elasticity photosensitive resin and preparation method thereof |
| CN109777024B (en) * | 2019-01-08 | 2021-06-01 | 宁波浙创科技有限公司 | SLA elastic photosensitive resin for 3D printing and preparation method thereof |
| CN111377738A (en) * | 2020-02-11 | 2020-07-07 | 甘肃机电职业技术学院（甘肃省机械工业学校、甘肃省机械高级技工学校） | Preparation method of ceramic material for 3d printing |
| CN114634613A (en) * | 2022-03-21 | 2022-06-17 | 北京印刷学院 | Color 3D printing material and application thereof |
| CN115124879A (en) * | 2022-05-30 | 2022-09-30 | 无锡市科虹标牌有限公司 | Production method of LED display lamp source softening diffusion diaphragm |
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