CN111303756A - Surface photocuring protective paint for 3D printing ink and preparation method thereof - Google Patents
Surface photocuring protective paint for 3D printing ink and preparation method thereof Download PDFInfo
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- CN111303756A CN111303756A CN202010290985.1A CN202010290985A CN111303756A CN 111303756 A CN111303756 A CN 111303756A CN 202010290985 A CN202010290985 A CN 202010290985A CN 111303756 A CN111303756 A CN 111303756A
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- protective paint
- acrylate
- ink
- hyperbranched
- acrylate oligomer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a 3D ink surface light-cured protective paint and a preparation method thereof, wherein the 3D ink surface light-cured protective paint is prepared from the following components in percentage by weight: 40-50% of polyurethane acrylate oligomer; 10-25% of hyperbranched polyurethane acrylate oligomer; 25-30% of reactive diluent; 5-10% of a photoinitiator; 0.1 to 1 percent of auxiliary agent. The surface photocuring protective paint for the 3D printing ink has excellent flexibility and wear resistance, and is very suitable for being used as photocuring paint.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a 3D ink surface photocuring protective paint and a preparation method thereof.
Background
Ultraviolet light curing (solidification) is one of radiation curing technologies, is a new 'green' technology which develops rapidly, and is an energy-saving and environment-friendly coating developed in century years.
The hyperbranched polymer has the advantages of high solubility and reactivity, low overall viscosity and the like, and is widely applied to the field of coatings. Hyperbranched aliphatic polyesters are one of a few hyperbranched polymers that are currently commercially produced worldwide. Hyperbranched aliphatic polyesters have lower viscosity and higher UV cure rate than linear polyesters of similar relative molecular mass.
Therefore, the research on the light-cured protective paint containing the hyperbranched polyurethane acrylate becomes the development trend in the field of light-cured coatings at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a surface light-cured protective paint for 3D ink in a first aspect. The specific technical scheme is as follows:
A3D printing ink surface light-cured protective paint is prepared from the following components in percentage by weight:
40-50% of polyurethane acrylate oligomer;
10-25% of hyperbranched polyurethane acrylate oligomer;
25-30% of reactive diluent;
5-10% of a photoinitiator;
0.1 to 1 percent of auxiliary agent.
The invention provides a preparation method of a 3D ink surface photo-curing protective paint, which comprises the following steps:
synthesizing hyperbranched polyurethane acrylate oligomer;
and mixing and uniformly stirring the synthesized hyperbranched polyurethane acrylate oligomer, the reactive diluent, the photoinitiator and the auxiliary agent according to the weight percentage to obtain the surface photocuring protective paint for the 3D ink.
Compared with the prior art, the surface light-cured protective paint for the 3D printing ink prepared by the invention has the following advantages: 1. the hyperbranched polyurethane acrylate oligomer enables the cured coating to have good flexibility. 2. The hyperbranched polyurethane acrylate oligomer enables the cured coating to have good wear resistance.
Detailed Description
The following describes the technical aspects of the present invention in detail with reference to examples, but the present invention is not limited to these examples.
Before describing the embodiments, the following explanation is required:
the urethane acrylate oligomer used in each example of the present invention was a urethane acrylate oligomer obtained from taiwan changxing chemical engineering under product code 61856, 6123, 611B-85 or 6185.
The hyperbranched urethane acrylate oligomer used in each example of the present invention was a hyperbranched urethane acrylate oligomer with product code H20 available from Perstorp AB, sweden.
The auxiliaries used in the examples of the invention are those available from Bike, Germany under the product code BYK333, BYK306 or from Dongguan mountain under the plasticized product code UV 531.
Example 1:
step one, synthesizing hyperbranched polyurethane acrylate oligomer, which specifically comprises the following steps:
taking materials according to the following weight percentage: 25% of isophorone diisocyanate, 0.5% of dibutyltin dilaurate, 20% of hydroquinone, 25% of 2-hydroxyethyl acrylate and 29.5% of hyperbranched polyester. Adding metered isophorone diisocyanate, dibutyltin dilaurate and hydroquinone into a reaction container provided with a stirrer, a thermometer and a reflux condenser tube, dropwise adding metered acrylate into the reaction container within 0.5h, reacting at 35 ℃, measuring the NCO value of reactants every 0.5h until the NCO value reaches half of the initial reaction, and preparing a pre-product with an NCO group at one end and a double bond at the other end;
and (3) raising the temperature to 70 ℃, adding the hyperbranched acrylic ester into the pre-product within 0.5h, measuring the NCO value in the reactant every 0.5h until the NCO value is less than 0.5%, and evaporating the solvent to obtain the transparent hyperbranched polyurethane acrylic ester oligomer.
Taking materials according to the following weight percentage: 10% of hyperbranched polyurethane acrylate oligomer, 50% of polyurethane acrylate oligomer, 30% of furfuryl acrylate tetroxide, 9% of 2-hydroxy-2-methyl-1-phenyl-1-acetone and 1% of auxiliary agent, and mixing and uniformly stirring the components to obtain the surface light-cured protective paint for the 3D ink.
Example 2
Example 2 differs from example 1 only in that in step one, 2-hydroxyethyl acrylate is replaced by 2-hydroxyethyl methacrylate.
Example 3
Example 2 differs from example 1 only in that in step one, 2-hydroxyethyl acrylate is replaced by 2-hydroxypropyl methacrylate.
Example 4:
step one, synthesizing hyperbranched polyurethane acrylate oligomer, which specifically comprises the following steps:
taking materials according to the following weight percentage: 30% of hexamethylene diisocyanate, 0.05% of dibutyltin dilaurate, 25% of hydroquinone, 19.55% of 2-hydroxypropyl acrylate and 25.4% of hyperbranched polyester. Adding metered isophorone diisocyanate, dibutyltin dilaurate and hydroquinone into a reaction container provided with a stirrer, a thermometer and a reflux condenser tube, dropwise adding metered acrylate into the reaction container within 0.5h, reacting at 35 ℃, measuring the NCO value of reactants every 0.5h until the NCO value reaches half of the initial reaction, and preparing a pre-product with an NCO group at one end and a double bond at the other end;
and (3) raising the temperature to 70 ℃, adding the hyperbranched acrylic ester into the pre-product within 0.5h, measuring the NCO value in the reactant every 0.5h until the NCO value is less than 0.5%, and evaporating the solvent to obtain the transparent hyperbranched polyurethane acrylic ester oligomer.
Taking materials according to the following weight percentage: 20% of hyperbranched polyurethane acrylate oligomer, 45% of polyurethane acrylate oligomer, 25% of ethoxy ethyl acrylate, 9.9% of 1-hydroxycyclohexyl phenyl ketone and 0.1% of auxiliary agent, and mixing and uniformly stirring the components to obtain the surface light-cured protective paint for the 3D ink.
Example 5
Example 5 differs from example 4 only in that in step one, 2-hydroxypropyl acrylate is replaced with 3-hydroxypropyl acrylate.
Example 6
Example 6 differs from example 4 only in that in step one, 2-hydroxypropyl acrylate is replaced with 3-hydroxypropyl methacrylate.
Example 7
Example 7 differs from example 4 only in the first step, replacing 2-hydroxypropyl acrylate with 3-hydroxybutyl methacrylate.
Example 8:
step one, synthesizing hyperbranched polyurethane acrylate oligomer, which specifically comprises the following steps:
taking materials according to the following weight percentage: 30% of dicyclohexyl methane diisocyanate, 0.3% of dibutyltin dilaurate, 15% of hydroquinone, 24.7% of 3-hydroxybutyl acrylate and 30% of hyperbranched polyester. Adding metered isophorone diisocyanate, dibutyltin dilaurate and hydroquinone into a reaction container provided with a stirrer, a thermometer and a reflux condenser tube, dropwise adding metered acrylate into the reaction container within 0.5h, reacting at 35 ℃, measuring the NCO value of reactants every 0.5h until the NCO value reaches half of the initial reaction, and preparing a pre-product with an NCO group at one end and a double bond at the other end;
and (3) raising the temperature to 70 ℃, adding the hyperbranched acrylic ester into the pre-product within 0.5h, measuring the NCO value in the reactant every 0.5h until the NCO value is less than 0.5%, and evaporating the solvent to obtain the transparent hyperbranched polyurethane acrylic ester oligomer.
Taking materials according to the following weight percentage: 25% of hyperbranched polyurethane acrylate oligomer, 40% of polyurethane acrylate oligomer, 30% of 2-dimethylpropyl diacrylate, 5% of 2,4, 6-trimethylbenzoyl-diphenylphosphineoxide and 1% of an auxiliary agent, and mixing and uniformly stirring the components to obtain the surface photocuring protective paint for the 3D ink.
Example 9:
example 9 differs from example 8 only in that in step one, 4-hydroxybutyl acrylate is used instead of 3-hydroxybutyl acrylate.
Example 10:
example 10 differs from example 8 only in the first step, replacing 3-hydroxybutyl acrylate with 4-hydroxybutyl methacrylate.
The testing process comprises the following steps:
the surface light-cured protective paint of the 3D printing ink prepared in the examples 1-10 is respectively coated on the surface of the 3D printing ink, the thickness is controlled to be 350 mu m, the coating is cured by an ultraviolet curing machine, the curing capability is controlled to be 300mJ/cm2, and finally the sample plate is taken out to test the flexibility, the wear resistance and the yellowing resistance of the coating.
Wherein: flexibility test according to the paint film flexibility test method of GB/T1731-1993, abrasion resistance test according to GB/T1768-1989, paint film abrasion resistance test method, and paint film yellowing resistance test according to GB/T1995. The specific test results are shown in the following table:
therefore, the wear resistance, flexibility, curing rate and yellowing resistance of the surface photocuring protective paint for the 3D ink of each embodiment of the invention can meet the requirements.
In addition, as can be seen from the test result table, when the amount of the hyperbranched urethane acrylate oligomer is increased to 20%, the abrasion resistance and the curing rate are obviously improved.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The surface photocuring protective paint for the 3D printing ink is characterized by being prepared from the following components in percentage by weight:
40-50% of polyurethane acrylate oligomer;
10-25% of hyperbranched polyurethane acrylate oligomer;
25-30% of reactive diluent;
5-10% of a photoinitiator;
0.1 to 1 percent of auxiliary agent.
2. The light-cured protective paint on the surface of 3D ink according to claim 1, wherein the hyperbranched polyurethane acrylate oligomer is prepared from the following components in percentage by weight:
25-30% of diisocyanate;
15-25% of acrylic ester.
15-25% of dihydric alcohol;
25-30% of hyperbranched polyester;
0.05-0.5% of organic metal catalyst.
3. The light-cured protective paint on the surface of 3D ink according to claim 1, wherein the reactive diluent comprises one or more of furfuryl tetraoxide acrylate, ethoxy ethyl acrylate, 2-dimethyl propyl acrylate diacrylate and isobornyl acrylate.
4. The light-cured protective paint on the surface of the 3D ink according to claim 1, wherein the photoinitiator comprises one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide.
5. The 3D ink surface light-curable protective paint of claim 1, wherein the phosphate ester comprises 2-hydroxyethyl methacrylate phosphate.
6. The light-cured protective paint on the surface of 3D ink according to claim 2, wherein the diisocyanate comprises one or more of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.
7. The 3D ink surface light-curable protective paint of claim 2, wherein the glycol comprises hydroquinone and the organometallic catalyst comprises dibutyltin dilaurate.
8. The light-cured protective paint on the surface of the 3D ink as claimed in claim 2, wherein the acrylate comprises one or more of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate.
9. A method for preparing a protective paint for surface photocuring of 3D ink according to claim 1, comprising the steps of:
synthesizing hyperbranched polyurethane acrylate oligomer;
and mixing and uniformly stirring the synthesized hyperbranched polyurethane acrylate oligomer, the reactive diluent, the photoinitiator and the auxiliary agent according to the weight percentage to obtain the surface photocuring protective paint for the 3D ink.
10. The method of preparing a protective paint for surface photocuring of 3D ink according to claim 9, wherein the synthetic hyperbranched urethane acrylate oligomer comprises:
adding diisocyanate, an organic metal catalyst and dihydric alcohol which are measured in percentage by weight into a reaction container provided with a stirrer, a thermometer and a reflux condenser tube, dropwise adding the measured acrylate into the reaction container within 0.5h, reacting at 25-45 ℃, measuring the NCO value of reactants every 0.5h until the NCO value reaches half of the initial reaction, and preparing a pre-product with an NCO group at one end and a double bond at the other end;
and (3) raising the temperature to 60-80 ℃, adding the hyperbranched polyester into the pre-product within 0.5h, measuring the NCO value in the reactant every 0.5h until the NCO value is less than 0.5%, and evaporating the solvent to obtain the transparent hyperbranched polyurethane acrylate oligomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010290985.1A CN111303756A (en) | 2020-04-14 | 2020-04-14 | Surface photocuring protective paint for 3D printing ink and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010290985.1A CN111303756A (en) | 2020-04-14 | 2020-04-14 | Surface photocuring protective paint for 3D printing ink and preparation method thereof |
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| CN111303756A true CN111303756A (en) | 2020-06-19 |
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| CN202010290985.1A Pending CN111303756A (en) | 2020-04-14 | 2020-04-14 | Surface photocuring protective paint for 3D printing ink and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740265A (en) * | 2013-12-31 | 2014-04-23 | 佛山佛塑科技集团股份有限公司 | Ultraviolet curable coating for hardening treatment of plastic surfaces and preparation method of ultraviolet curable coating |
| CN107759757A (en) * | 2017-10-30 | 2018-03-06 | 北京理工大学 | The preparation method and ultraviolet-curing paint of a kind of ultra-branched polyurethane acrylate |
-
2020
- 2020-04-14 CN CN202010290985.1A patent/CN111303756A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740265A (en) * | 2013-12-31 | 2014-04-23 | 佛山佛塑科技集团股份有限公司 | Ultraviolet curable coating for hardening treatment of plastic surfaces and preparation method of ultraviolet curable coating |
| CN107759757A (en) * | 2017-10-30 | 2018-03-06 | 北京理工大学 | The preparation method and ultraviolet-curing paint of a kind of ultra-branched polyurethane acrylate |
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Application publication date: 20200619 |
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