CN112029042A - Photosensitive material for 3D printing and preparation method thereof - Google Patents
Photosensitive material for 3D printing and preparation method thereof Download PDFInfo
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- CN112029042A CN112029042A CN201911235046.0A CN201911235046A CN112029042A CN 112029042 A CN112029042 A CN 112029042A CN 201911235046 A CN201911235046 A CN 201911235046A CN 112029042 A CN112029042 A CN 112029042A
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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
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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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
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a photosensitive material for 3D printing and a preparation method thereof, wherein the photosensitive material comprises the following raw materials in parts by weight: 10-25 parts of acrylic resin, 60-75 parts of reactive diluent, 10-20 parts of toughening agent, 1-5 parts of photoinitiator and 0.05-0.1 part of auxiliary agent, wherein the acrylic resin, the reactive diluent, the toughening agent, the photoinitiator and the auxiliary agent are weighed according to the preset weight parts, mixed and stirred in a dispersion machine, uniformly dispersed for 20-40 minutes, and the temperature is controlled at 40-60 ℃ in the stirring process to obtain the UV photocuring photosensitive material. The photosensitive material prepared by the invention has the advantages of high curing speed, good product storage stability, difficult deformation of a large printed model, excellent bending performance, capability of directly printing an elastic model and suitability for DLP (digital light processing) rapid prototyping desktop-level 3D printing equipment.
Description
Technical Field
The invention relates to a photosensitive material, in particular to a UV (ultraviolet) photocuring photosensitive material for DLP (digital light processing) rapid prototyping desktop-level 3D printing equipment and a preparation method thereof.
Background
The 3D printing technology using photosensitive resin as a printing material mainly includes: stereolithography rapid prototyping (SLA), DLP projection three-dimensional printing (DLP) and ultra-thin layer thickness photosensitive resin jet molding (Connex500 systems Objet geometry). The printing process is to determine the three-dimensional model in a computer and then deliver the three-dimensional model to a 3D printer, and ultraviolet rays are adopted to irradiate liquid photosensitive resin in the printing process, so that the three-dimensional model is formed by stacking layers.
Photosensitive resin for 3D printing needs to be rapidly cured under the exposure condition of a 3D printer, and in addition, the printing process of the printer needs to be met, and the photosensitive resin has certain fluidity. These are the basic requirements that photosensitive resins can be used in 3D printers. At present, the photosensitive resin for 3D printers in China is single in variety and mainly is resin with high hardness, but the resin has the defects of insufficient toughness, poor impact resistance and fragility, and the high-toughness 3D printing photosensitive resin is a new research and development direction of 3D printing materials.
Disclosure of Invention
The invention aims to provide a photosensitive material for 3D printing and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the photosensitive material for 3D printing is composed of the following raw materials in parts by weight:
10-25 parts of acrylic resin, 60-75 parts of reactive diluent, 10-20 parts of toughening agent, 1-5 parts of photoinitiator and 0.05-0.1 part of auxiliary agent.
The acrylic resin is one or a mixture of more than two of polyurethane acrylate, polyester acrylate and modified epoxy acrylate.
The reactive diluent is tripropylene glycol diacrylate, hexanediol diacrylate, bisphenol A diacrylate, tetratriethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, cyclotrimethylolpropane formal acrylate, isobornyl acrylate, 4-hydroxybutyl vinyl ether, 4-vinylcyclohexene oxide, vinylpyrrolidone, diethylene glycol divinyl ether, 4-vinylcyclohexene oxide, cyclic ether (3,3' - [ oxybis ] bis [ 3-ethyl ] oxetane, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3- [ (2-ethylhexyloxy) methyl ] oxetane, or mixtures thereof, 1, 4 bis [ (3-ethyl-3-oxymethylene oxetane) methyl ] benzene) and a cyclic lactone (propylene carbonate).
The toughening agent is one or two of 3-ethyl-3-oxetanemethanol and 3-methyl-3-hydroxymethyl oxetane.
The photoinitiator is one or two of acetophenone derivatives and aromatic ketones, wherein the acetophenone derivatives comprise 1-hydroxycyclohexylacetophenone, alpha-dimethyl-alpha-hydroxyacetophenone and p-isopropylphenyl-2-hydroxydimethyl acetone-1, and the aromatic ketones comprise benzophenone, chlorinated benzophenone, acrylated benzophenone, 4-phenylbenzophenone, 2-chlorinated thioxanthone, isopropyl thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, dichloro thioxanthone and 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide.
The auxiliary agent comprises one or a mixture of more than two of TEGO Airex900, TEGO Airex910, TEGO Airex920, TEGO Airex932, TEGO Airex940, TEGO Airex945 and TEGO Foamex N.
A preparation method of a photosensitive material for 3D printing is characterized by comprising the following steps:
weighing acrylic resin, reactive diluent, toughening agent, photoinitiator and auxiliary agent according to the preset weight parts, putting the acrylic resin, the reactive diluent, the toughening agent, the photoinitiator and the auxiliary agent into a dispersion machine for mixing and stirring, uniformly dispersing for 20-40 minutes, and controlling the temperature to be 40-60 ℃ in the stirring process to obtain the UV photocuring photosensitive material.
The photosensitive material prepared by the invention has the advantages of high curing speed, good product storage stability, difficult deformation of a large printed model, excellent bending performance, capability of directly printing an elastic model and suitability for DLP (digital light processing) rapid prototyping desktop-level 3D printing equipment.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to further understand the features and technical means of the invention and achieve specific objects and functions.
Example one
A photosensitive material for 3D printing comprises the following components in parts by weight:
25 parts of acrylic resin;
65 parts of a reactive diluent;
10 parts of a toughening agent;
5 parts of a photoinitiator;
0.1 part of an auxiliary agent.
The acrylic resin is modified epoxy acrylate.
The active diluent is a mixture of tripropylene glycol diacrylate, trimethylolpropane triacrylate and hydroxyethyl methacrylate in a ratio of 3:3: 1.
The toughening agent is a mixture of 3-ethyl-3-oxetanemethanol and 3-methyl-3-hydroxymethyl oxetane in a ratio of 1: 1.
The photoinitiator is 4-phenyl benzophenone.
The auxiliary agent is TEGO Airex 945.
The UV light-cured photosensitive material can be prepared by the process commonly adopted in the field, the materials are weighed according to the parts by weight and are uniformly dispersed by stirring for 30 minutes by a dispersion machine, and the temperature is controlled at 50 ℃ to obtain the UV light-cured photosensitive material.
Example two
A photosensitive material for 3D printing comprises the following components in parts by weight:
15 parts of acrylic resin;
75 parts of a reactive diluent;
10 parts of a toughening agent;
4 parts of a photoinitiator;
0.1 part of an auxiliary agent;
the acrylic resin is urethane acrylate.
The reactive diluent is a mixture of tripropylene glycol diacrylate, hexanediol diacrylate, bisphenol A diacrylate, tetraethylene glycol triacrylate and trimethylolpropane triacrylate.
The toughening agent is a mixture of 3-ethyl-3-oxetanemethanol and 3-methyl-3-hydroxymethyl oxetane in a ratio of 2: 1.
The photoinitiator is alpha-dimethyl-alpha-hydroxyacetophenone.
The auxiliary agent is TEGO Airex 910.
The UV light-cured photosensitive material can be prepared by the process commonly adopted in the field, the materials are weighed according to the parts by weight and are uniformly dispersed by stirring for 35 minutes by a dispersion machine, and the temperature is controlled at 55 ℃ to obtain the UV light-cured photosensitive material.
EXAMPLE III
A photosensitive material for 3D printing comprises the following components in parts by weight:
25 parts of acrylic resin;
60 parts of a reactive diluent;
15 parts of a toughening agent;
3.5 parts of a photoinitiator;
0.1 part of an auxiliary agent;
the acrylic resin is polyester acrylate.
The reactive diluent is a mixture of vinyl pyrrolidone and diethylene glycol divinyl ether.
The toughening agent is a mixture of 3-ethyl-3-oxetanemethanol and 3-methyl-3-hydroxymethyl oxetane in a ratio of 3: 1.
The photoinitiator is 2-thioxanthone chloride or isopropyl thioxanthone.
The auxiliary agent is TEGO Airex 920.
The UV light-cured photosensitive material of this example was prepared by the process commonly used in the art by weighing the above materials in parts by weight, stirring with a dispersion machine for 38 minutes to disperse uniformly, and controlling the temperature at 58 ℃ to obtain the UV light-cured photosensitive material.
Example four
A photosensitive material for 3D printing comprises the following components in parts by weight:
25 parts of acrylic resin;
60 parts of a reactive diluent;
15 parts of a toughening agent;
3.5 parts of a photoinitiator;
0.1 part of an auxiliary agent;
the acrylic resin is polyester acrylate.
The active diluent is a mixture of tripropylene glycol diacrylate, hexanediol diacrylate, bisphenol A diacrylate, tetraethylene glycol triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, cyclic trimethylolpropane formal acrylate, isobornyl acrylate, 4-hydroxybutyl vinyl ether, 4-vinyl epoxycyclohexane and vinylpyrrolidone.
The toughening agent is a mixture of 3-ethyl-3-oxetanemethanol and 3-methyl-3-hydroxymethyl oxetane in a ratio of 3: 2.
The photoinitiator is 4-phenyl benzophenone.
The auxiliary agent is TEGO Airex 945.
The UV light-cured photosensitive material of this example was prepared by the process commonly used in the art by weighing the above materials in parts by weight, stirring with a dispersion machine for 38 minutes to disperse uniformly, and controlling the temperature at 58 ℃ to obtain the UV light-cured photosensitive material.
EXAMPLE five
A photosensitive material for 3D printing comprises the following components in parts by weight:
25 parts of acrylic resin;
60 parts of a reactive diluent;
0 part of a toughening agent;
3.5 parts of a photoinitiator;
0.1 part of an auxiliary agent;
the acrylic resin is polyester acrylate.
The active diluent is a mixture of tripropylene glycol diacrylate, hexanediol diacrylate, bisphenol A diacrylate, tetraethylene glycol triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, cyclic trimethylolpropane formal acrylate, isobornyl acrylate, 4-hydroxybutyl vinyl ether, 4-vinyl epoxycyclohexane and vinylpyrrolidone.
The toughener being 0 means that no toughener is added for this set of experiments.
The photoinitiator is 4-phenyl benzophenone.
The auxiliary agent is TEGO Airex 945.
The UV light-cured photosensitive material of this example was prepared by the process commonly used in the art by weighing the above materials in parts by weight, stirring with a dispersion machine for 38 minutes to disperse uniformly, and controlling the temperature at 58 ℃ to obtain the UV light-cured photosensitive material.
[ comparative experiment ]
The photosensitive resins prepared in examples 1 to 5 were printed on test strips of the same size using the same printing apparatus, while 2 types of high-toughness photosensitive resins currently used in general were used as a comparison, and the comparative materials were also printed on test strips of the same size using the same printing apparatus. The test strip after printing and forming is subjected to mechanical test, and the data are as follows:
| group of | Yield strength (MPa) | Tensile strength (MPa) | Elongation at Break (%) |
| Example 1 | 338 | 533 | 15.1 |
| Example 2 | 359 | 523 | 13.9 |
| Example 3 | 341 | 519 | 14.0 |
| Example 4 | 356 | 510 | 13.8 |
| Example 5 (blank) | 179 | 286 | 5.5 |
| Comparative example 1 | 245 | 390 | 8.5 |
| Comparative example 2 | 232 | 423 | 7.5 |
From the data, the finished material printed and molded by the 3D printing photosensitive resin has better mechanical strength and toughness.
Although the present invention has been described in detail with reference to the embodiments, it will be apparent to those skilled in the art that modifications, equivalents, improvements, and the like can be made in the technical solutions of the foregoing embodiments or in some of the technical features of the foregoing embodiments, but those modifications, equivalents, improvements, and the like are all within the spirit and principle of the present invention.
Claims (7)
1. The photosensitive material for 3D printing is characterized by comprising the following raw materials in parts by weight:
10-25 parts of acrylic resin, 60-75 parts of reactive diluent, 10-20 parts of toughening agent, 1-5 parts of photoinitiator and 0.05-0.1 part of auxiliary agent.
2. The photosensitive material for 3D printing according to claim 1, wherein the acrylic resin is one or a mixture of two or more of urethane acrylate, polyester acrylate, and modified epoxy acrylate.
3. The photosensitive material for 3D printing according to claim 1, wherein the reactive diluent is tripropylene glycol diacrylate, hexanediol diacrylate, bisphenol a diacrylate, tetraethylene glycol triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, cyclotrimethylolpropane formal acrylate, isobornyl acrylate, 4-hydroxybutyl vinyl ether, 4-vinylepoxycyclohexane, vinylpyrrolidone, diethylene glycol divinyl ether, 4-vinylepoxycyclohexane, cyclic ether (3,3' - [ oxybis ] dimethylene ] bis [ 3-ethyl ] oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- [ (2-ethylhexyloxy) methyl ] oxetane, 1, 4-bis [ (3-ethyl-3-oxymethyleneoxetanyl) methyl ] benzene) and a cyclic lactone (propylene carbonate).
4. The photosensitive material for 3D printing according to claim 1, wherein the toughening agent is one or both of 3-ethyl-3-oxetanemethanol and 3-methyl-3-hydroxymethyloxetane.
5. The photosensitive material for 3D printing according to claim 1, wherein the photoinitiator is one or both of acetophenone derivatives and aromatic ketones, wherein the acetophenone derivatives include 1-hydroxycyclohexylacetophenone, α -dimethyl- α -hydroxyacetophenone, p-isopropylphenyl-2-hydroxydimethyl acetone-1, and the aromatic ketones include benzophenone, chlorinated benzophenone, acrylated benzophenone, 4-phenylbenzophenone, 2-chlorinated thioxanthone, isopropyl thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, dichlorothioxanthone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide.
6. The photosensitive material for 3D printing according to claim 1, wherein the auxiliary agent comprises one or a mixture of two or more of TEGO Airex900, TEGO Airex910, TEGO Airex920, TEGO Airex932, TEGO Airex940, TEGO Airex945, and TEGO Foamex N.
7. A method for preparing a photosensitive material for 3D printing according to any one of claims 1 to 6, comprising the steps of:
weighing acrylic resin, reactive diluent, toughening agent, photoinitiator and auxiliary agent according to the preset weight parts, putting the acrylic resin, the reactive diluent, the toughening agent, the photoinitiator and the auxiliary agent into a dispersion machine for mixing and stirring, uniformly dispersing for 20-40 minutes, and controlling the temperature to be 40-60 ℃ in the stirring process to obtain the UV photocuring photosensitive material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911235046.0A CN112029042A (en) | 2019-12-05 | 2019-12-05 | Photosensitive material for 3D printing and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911235046.0A CN112029042A (en) | 2019-12-05 | 2019-12-05 | Photosensitive material for 3D printing and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113754836A (en) * | 2021-09-26 | 2021-12-07 | 泉州洛江扶摇三维科技有限公司 | Preparation method of 3D printing photosensitive resin based on recycled PET bottle flakes |
| CN114272144A (en) * | 2021-12-30 | 2022-04-05 | 浙江闪铸三维科技有限公司 | Rapid photocuring printing material and preparation method thereof |
| CN114763400A (en) * | 2021-01-13 | 2022-07-19 | 中国石油化工股份有限公司 | Flexible photosensitive resin and preparation method thereof, and 3D printing product and preparation method thereof |
| CN114986902A (en) * | 2022-06-07 | 2022-09-02 | 丽水学院 | Preparation method of high-performance DLP-3D printing material applied to oral medical field |
| CN116099984A (en) * | 2023-04-12 | 2023-05-12 | 邢台速锐网络科技有限公司 | 3D printing sand mold product material and 3D printing sand mold method and device |
-
2019
- 2019-12-05 CN CN201911235046.0A patent/CN112029042A/en active Pending
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| 史玉升等著: "《3D打印材料(上册)》", 31 March 2019, 华中科技大学出版社 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114763400A (en) * | 2021-01-13 | 2022-07-19 | 中国石油化工股份有限公司 | Flexible photosensitive resin and preparation method thereof, and 3D printing product and preparation method thereof |
| CN113754836A (en) * | 2021-09-26 | 2021-12-07 | 泉州洛江扶摇三维科技有限公司 | Preparation method of 3D printing photosensitive resin based on recycled PET bottle flakes |
| CN114272144A (en) * | 2021-12-30 | 2022-04-05 | 浙江闪铸三维科技有限公司 | Rapid photocuring printing material and preparation method thereof |
| CN114272144B (en) * | 2021-12-30 | 2023-11-21 | 浙江闪铸三维科技有限公司 | Rapid photo-curing printing material and preparation method thereof |
| CN114986902A (en) * | 2022-06-07 | 2022-09-02 | 丽水学院 | Preparation method of high-performance DLP-3D printing material applied to oral medical field |
| CN116099984A (en) * | 2023-04-12 | 2023-05-12 | 邢台速锐网络科技有限公司 | 3D printing sand mold product material and 3D printing sand mold method and device |
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Application publication date: 20201204 |