CN112940583A - Photosensitive resin composition for photocuring coating and photocuring coating prepared from same - Google Patents
Photosensitive resin composition for photocuring coating and photocuring coating prepared from same Download PDFInfo
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- CN112940583A CN112940583A CN202110129615.4A CN202110129615A CN112940583A CN 112940583 A CN112940583 A CN 112940583A CN 202110129615 A CN202110129615 A CN 202110129615A CN 112940583 A CN112940583 A CN 112940583A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
The invention relates to the field of photocuring coatings, and discloses a photosensitive resin composition for a photocuring coating and a photocuring coating prepared from the photosensitive resin composition. The photosensitive resin composition comprises, by weight, 40-100 parts of epoxy resin, 0-20 parts of a toughening agent, 0-10 parts of a cationic photoinitiator, 0-5 parts of a free radical photoinitiator and 0-1 part of a leveling agent. The coating prepared by using the photosensitive resin composition can be quickly crosslinked and cured after being irradiated by ultraviolet light, and the cured coating has excellent performances of yellowing resistance, abrasion resistance and the like, has no oxygen inhibition and has excellent adhesive force to most base materials.
Description
Technical Field
The invention belongs to the field of photocureable coatings, and relates to a photosensitive resin composition for photocureable coatings on the surfaces of different base materials, in particular to a photosensitive resin composition for photocureable coatings and a photocureable coating prepared from the photosensitive resin composition.
Background
The photocuring coating is a novel environment-friendly coating, has the characteristics of high curing speed (the photocuring coating can be cured only by ultraviolet light irradiation within a few seconds), energy saving (compared with a thermosetting coating and a powder coating, the energy consumption is only 1/5-1/10), environmental friendliness (the photocuring coating does not contain a solvent, the emission of VOC is almost zero, and the environment is not polluted), and the like, is widely applied to the industrial field and the electronic field, is rapidly developed in recent years, and becomes a product with larger sales volume in the photocuring industrial field. Currently, the photocurable coating has been developed from the conventional one only suitable for wood substrates to the one suitable for various substrates such as plastics, glass, metal, etc., and is being developed toward functionalization. Most of raw materials used for photocuring coatings in the market at present are free radical photosensitive resin and photoinitiator, so that the coatings prepared by ultraviolet irradiation usually have excellent adhesive force only for a certain specific base material, but are not suitable for other base materials accompanied with oxygen inhibition, the application range of products is narrow, and the coatings are difficult to cure and have sticky surfaces and cannot be used due to the existence of the oxygen inhibition. Therefore, the development of the photosensitive resin composition for the photocureable coating which has no oxygen inhibition, can be quickly crosslinked and cured, has excellent performances of yellowing resistance, abrasion resistance and the like of the cured coating and has excellent adhesive force to most of base materials is worthy, and has very important significance for the market of the photocureable coating field.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the photosensitive resin composition for the photocuring coating, which can be quickly crosslinked and cured, has yellowing resistance, abrasion resistance and no oxygen inhibition, and has excellent adhesive force to most of base materials, and the photocuring coating prepared by the photosensitive resin composition.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the photosensitive resin composition for the photocuring coating comprises epoxy resin, a toughening agent, a cationic photoinitiator, a free radical photoinitiator and a leveling agent; preferably, the photosensitive resin composition consists of epoxy resin, a toughening agent, a cationic photoinitiator, a free radical photoinitiator and a leveling agent; the photosensitive resin composition comprises, by weight, 40-100 parts of epoxy resin, 0-20 parts of a toughening agent, 0-10 parts of a cationic photoinitiator, 0-5 parts of a free radical photoinitiator and 0-1 part of a leveling agent, wherein the components of an acrylate oligomer, the toughening agent, the cationic photoinitiator, the free radical photoinitiator and the leveling agent are not 0; further preferably, the photosensitive resin composition comprises, by weight, 100 parts of an epoxy resin, 5-15 parts of a toughening agent, 2-8 parts of a cationic photoinitiator, 0.2-2 parts of a radical photoinitiator, and 0.1-0.5 part of a leveling agent.
In the present invention, the epoxy resin is one or more of alicyclic epoxy resin, bisphenol A type epoxy resin, and aliphatic epoxy resin, preferably alicyclic epoxy resin, such as 3,4-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate (TTA21), bis ((3, 4-epoxycyclohexyl) methyl) adipate (TTA26), poly [ (2-oxiranyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol ether (3:1) (TTA3150), 1, 2-epoxy-4-vinylcyclohexane (TTA11), 3, 4-epoxycyclohexylmethylmethacrylate (TTA15), 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] heptane (TTA20), 4-vinyl-1-cyclohexene diepoxide (TTA22), dicyclopentadiene diepoxide (TTA27), tetrahydroindene diepoxide (TTA28), 3,4,3 ', 4' -diepoxybicyclohexane (TTA800), and more preferably tetrahydroindene diepoxide (TTA 28).
In the present invention, the toughening agent is polyester polyol or polyether polyol, such as one or more of polycaprolactone polyol, polyester polyol and polyether polyol, and is more preferably selected from polycaprolactone polyol.
In the present invention, the cationic photoinitiator is an onium salt, such as one or more of triarylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, and diaryliodonium salts, and is more preferably selected from triarylsulfonium hexafluorophosphate (TTA UV-692).
In the invention, the free radical photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.
In the invention, the flatting agent is an organic silicon flatting agent.
The invention discloses application of the photosensitive resin composition for the photocuring coating in preparation of the photocuring coating, wherein the photocuring coating is prepared on the surfaces of different base materials, the base materials are plastic, glass, metal and other materials, preferably, the base materials are PP, PET, PVC, PMMA, glass, copper materials, tinplate and other materials. On the surfaces of a plurality of base materials, the composition can be quickly crosslinked and cured, has yellowing resistance and abrasion resistance, does not have oxygen inhibition and has excellent adhesive force to most base materials.
The invention has the following characteristics
In the formula of the invention, alicyclic epoxy resin, preferably tetrahydroindene diepoxide (TTA28), is used as main resin, and toughening agents such as polycaprolactone polyol are combined, so that the prepared photosensitive resin composition has the advantages of high curing speed, no oxygen inhibition in the curing process, yellowing resistance and abrasion resistance of the cured coating, and excellent adhesive force to most of substrates. The toughening agent is added in the formula, so that a coating cured by the photosensitive resin composition has good toughness and higher impact resistance. The leveling agent is added in the formula, so that the wettability of the coating on a base material can be improved, the leveling agent can adjust the surface tension, homogenize the coating, and is combined with the toughening agent, so that the phenomena of orange peel, shrinkage cavity and the like after a winding bar is subjected to blade coating are reduced, and the cured coating has a flat and smooth appearance.
Drawings
FIG. 1 is a photograph of the coating before and after testing of example four;
FIG. 2 is a photograph of a prior art coating before and after testing.
Detailed Description
The raw materials for the photosensitive resin composition of the present invention can be produced by an existing or conventional method or can be commercially available. The photosensitive resin composition comprises 40-100 parts of epoxy resin, 0-20 parts of a toughening agent, 0-10 parts of a cationic photoinitiator, 0-5 parts of a free radical photoinitiator and 0-1 part of a leveling agent, wherein the components of the acrylate oligomer, the toughening agent, the cationic photoinitiator, the free radical photoinitiator and the leveling agent are not 0.
The photosensitive resin composition of the present invention can be prepared by mixing and stirring given amounts of the alicyclic epoxy resin, the toughening agent, the cationic photoinitiator, the radical photoinitiator, and the leveling agent, and the stirring/mixing can be carried out using a conventional apparatus (high-speed shear disperser, planetary mixer, etc.), specifically, a conventional technique; the obtained photosensitive resin composition has excellent curability, can form a glue layer by ultraviolet irradiation, and can be suitably used as a photocuring coating on the surfaces of different substrates. The coating obtained by curing the photosensitive resin composition has the advantages of high curing speed, no oxygen inhibition in the curing process, yellowing resistance, abrasion resistance and excellent adhesive force to most base materials.
Characteristic evaluation (test method)
Oxygen inhibition effect: to compare whether the photosensitive resin composition is affected by oxygen inhibition during curing, photosensitive resin compositions of different formulations were respectively roll-coated on a glass substrate with a coating of the same thickness (20 μm) and under the same light source (UV mercury lamp) and light intensity (40 mW/cm)2) At the same irradiation height (150mm), the surface was completely dry and evaluated as √ when exposed to light for the same time (5 s); the surface finger touched a fingerprint but did not stick was rated as O; surface finger tack was rated x.
And (3) testing the adhesive force: in order to compare the adhesion of the photosensitive resin composition to the substrates, the adhesion rating of the subbing layer (thickness: 20 μm) on different substrates was measured according to the ISO2409-2013 paint and varnish cross-hatch test, and the adhesion rating of 1 or less was rated as √; the adhesion rating of more than 1 grade but 3 or less was rated as O; an adhesion rating of greater than 3 was rated as x.
And (3) wear resistance test: in order to compare the abrasion resistance of the photosensitive resin composition, a paint film abrader (model: JM-V, Shanghai modern environmental engineering service Co., Ltd.) was used. The abrasion resistance of the coating is tested according to ISO7784-2:1997 (rotating rubber grinding wheel method for determining abrasion resistance of paints and varnishes), the number of times of abrasion is more than or equal to 1000 times and the coating is evaluated as √; the number of rubbing was less than 1000 times but not less than 500 times and was evaluated as O without breakage; the number of abrasion was less than 500 times, and the breakage was evaluated as X.
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.
The details of the components used in the examples of the present invention and comparative examples are as follows.
A. Alicyclic epoxy resin: tetrahydroindene diepoxide (bicyclonoadiene diopoxide, TTA28, jiangsu titel new materials science and technology ltd); can be prepared by taking tetrahydroindene, dichloromethane, sodium carbonate and DPN (pyridine nucleotide diphosphate) as materials;
B. acrylate oligomer: polyester Acrylate (Polyester Acrylate, DR-E524, Happy materials industries, Inc.);
C. a toughening agent: polycaprolactone polyol (Polycaprolactone polyol, PCL-3057, new materials science and technology ltd for polymer kernels in Hunan);
D. cationic photoinitiator: 4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate & Bis (4- (diphenylsulfonium) phenyl) sulfide-Bis hexafluorophosphate (Diphenyl [4- (phenylthio) phenyl ] sulfonium hexafluorophosphate & Bis (4- (diphenylthio) phenyl) sulfate Bis (hexafluoro phosphate), TTA UV-692, butte thol new materials science co);
E. free radical photoinitiator: 2-hydroxy-2-methyl-1-phenyl-1-propanone (2-hydroxy-2-methyl-1-phenyl-1-acetone, 1173, new material for Tianjin Jiu Co., Ltd.);
F. leveling agent: polyether Modified Polydimethylsiloxane Copolymers (BYK-333, Dalian Cheng trade Co., Ltd.).
The photosensitive resin compositions of examples and comparative examples were prepared by the following methods:
component A, component B, component C in the amounts (unit: parts by weight) listed in Table 1 were mixed by ordinary stirring without solvent for 15 minutes; then, component D was added to the mixture, followed by stirring and mixing for 5 minutes, then component E was added, followed by stirring and mixing for 15 minutes, and finally component F was added, followed by stirring and mixing at room temperature, thereby preparing a photosensitive resin composition.
Table 1 example and comparative example formulations and performance testing
| A | B | C | D | E | F | Degree of surface dryness | Wear-resisting eraser | |
| Example one | 100 | 0 | 5 | 5 | 1 | 0.2 | ○ | ○ |
| Example two | 100 | 0 | 15 | 5 | 1 | 0.2 | √ | ○ |
| EXAMPLE III | 80 | 20 | 10 | 4 | 1 | 0.2 | ○ | √ |
| Example four | 100 | 0 | 10 | 5 | 1 | 0.2 | √ | √ |
| Comparative example 1 | 20 | 80 | 10 | 1 | 4 | 0.2 | × | ○ |
| Comparative example II | 0 | 100 | 10 | 0 | 5 | 0.2 | × | × |
| Comparative example III | 100* | 0 | 10 | 5 | 1 | 0.2 | √ | ○ |
| Comparative example four | 100 | 0 | 0 | 5 | 0 | 0.2 | √ | × |
| Comparative example five | 100 | 0 | 10 | 5 | 0 | 0 | √ | × |
Note that, in comparative example three, the alicyclic epoxy resin TTA28 was replaced with 3,4-Epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate (3,4-Epoxycyclohexylmethyl 3, 4-epoxycyclohexylamine Carboxylate, TTA21, jiangsu taier new material science and technology ltd).
Table 2 examples and comparative formulations adhesion test
Note that seven different substrates were selected for this test, and a wire bar was used to roll-coat a coating of the same thickness (20 μm) on the surface of the different substrates, using the same light source (UV mercury lamp), at the same intensity (40 mW/cm)2) And standing for 24h after exposure for the same time (10s) at the same irradiation height (150mm), and then carrying out an adhesion test.
Example four rub resistance test 2000 times unbroken, the photographs of the coating before and after the test are shown in figure 1; the abrasion resistance of the existing widely-used commercially-available epoxy photocureable coating is tested to be 860 times of damage, and photos of the coating before and after the test are shown in figure 2; the epoxy resin of example four was replaced with 3, 4-epoxycyclohexylmethylmethacrylate (TTA15), and the abrasion resistance was tested for 270 breaks with the remainder unchanged. Example three rub resistance test 1770 breaks; the toughener of example four was replaced with a linear polyester diol
(winning specialty chemistry (Shanghai) Co., Ltd.), and keeping the balance unchanged, and the abrasion resistance is 1250 times of breakage.
As shown in table 1, the photosensitive resin composition of the present invention, a coating obtained by ultraviolet irradiation curing, exhibits excellent properties, has a fast curing rate, does not have oxygen inhibition during curing, and the cured coating is resistant to yellowing and abrasion. As shown in Table 2, the photosensitive resin composition of the present invention produced a coating having excellent adhesion to most substrates. On the other hand, the comparison of the comparative examples shows that when the specific gravity of the alicyclic epoxy resin tetrahydroindene diepoxide (TTA28) component in the formula is more than or equal to 40%, the performance is greatly improved, and the performance is more excellent along with the increase of the TTA28 component, and when the formula is only TTA28, namely 100% of cationic component, the balance performance is optimal. The photosensitive resin composition has very important significance in the market of the field of photocureable coatings due to the excellent performance of the photosensitive resin composition after curing to form a film.
Claims (10)
1. The photosensitive resin composition for the photocuring coating is characterized by comprising epoxy resin, a toughening agent, a cationic photoinitiator, a free radical photoinitiator and a leveling agent.
2. The photosensitive resin composition for photocuring coating according to claim 1, which comprises, by weight, 40 to 100 parts of epoxy resin, 0 to 20 parts of toughening agent, 0 to 10 parts of cationic photoinitiator, 0 to 5 parts of radical photoinitiator, and 0 to 1 part of leveling agent, wherein the acrylate oligomer, the toughening agent, the cationic photoinitiator, the radical photoinitiator, and the leveling agent are not 0.
3. The photosensitive resin composition for photocuring coating according to claim 2, which comprises 100 parts by weight of an epoxy resin, 5 to 15 parts by weight of a toughening agent, 2 to 8 parts by weight of a cationic photoinitiator, 0.2 to 2 parts by weight of a radical photoinitiator, and 0.1 to 0.5 part by weight of a leveling agent.
4. The photosensitive resin composition for photocurable coating according to claim 1, wherein said epoxy resin is one or more of alicyclic epoxy resin, bisphenol a type epoxy resin, and aliphatic epoxy resin.
5. The photosensitive resin composition for photocurable coating according to claim 4, wherein said epoxy resin is a cycloaliphatic epoxy resin.
6. The photosensitive resin composition for photocurable coating according to claim 1, wherein said flexibilizer is polyester polyol or polyether polyol.
7. The photosensitive resin composition for photocurable coating according to claim 1, wherein said cationic photoinitiator is an onium salt; the free radical photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone; the leveling agent is an organic silicon leveling agent.
8. Use of the photosensitive resin composition for photocurable coating according to claim 1 for producing a photocurable coating.
9. A photocurable coating layer obtained by curing the photosensitive resin composition for photocurable coating layer according to claim 1.
10. Use of the photosensitive resin composition for photocured coating as set forth in claim 1 for producing a cured coating on the surface of a substrate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110129615.4A CN112940583B (en) | 2021-01-29 | 2021-01-29 | Photosensitive resin composition for photocuring coating and photocuring coating prepared from same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181581A (en) * | 2021-12-27 | 2022-03-15 | 深圳市法鑫忠信新材料有限公司 | High-hardness coating composition and preparation method thereof |
| CN115948111A (en) * | 2022-12-09 | 2023-04-11 | 中创新航科技股份有限公司 | Photocuring coating and battery comprising same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102385250A (en) * | 2011-06-29 | 2012-03-21 | 南昌大学 | Ultraviolet laser solidification rapid-prototyping photosensitive resin and manufacture method thereof |
| CN103571310A (en) * | 2013-11-15 | 2014-02-12 | 东北大学 | Free radical-cationic hybrid light curing coating and preparation method and application method thereof |
| WO2020209241A1 (en) * | 2019-04-09 | 2020-10-15 | Ｊｘｔｇエネルギー株式会社 | Curable composition and cured product of same |
-
2021
- 2021-01-29 CN CN202110129615.4A patent/CN112940583B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102385250A (en) * | 2011-06-29 | 2012-03-21 | 南昌大学 | Ultraviolet laser solidification rapid-prototyping photosensitive resin and manufacture method thereof |
| CN103571310A (en) * | 2013-11-15 | 2014-02-12 | 东北大学 | Free radical-cationic hybrid light curing coating and preparation method and application method thereof |
| WO2020209241A1 (en) * | 2019-04-09 | 2020-10-15 | Ｊｘｔｇエネルギー株式会社 | Curable composition and cured product of same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181581A (en) * | 2021-12-27 | 2022-03-15 | 深圳市法鑫忠信新材料有限公司 | High-hardness coating composition and preparation method thereof |
| CN115948111A (en) * | 2022-12-09 | 2023-04-11 | 中创新航科技股份有限公司 | Photocuring coating and battery comprising same |
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| CN112940583B (en) | 2022-09-13 |
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