CN110938374A - Boiling-resistant coating, preparation method and application thereof - Google Patents
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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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
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- 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
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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Abstract
The invention relates to the technical field of coating coatings, in particular to a boiling-resistant coating, a coating, and a preparation method and application thereof. The coating comprises the following components: alkoxysilane of at least three functionalities, basic silica sol, distilled water, acetic acid, solvent a, soft segment and silane coupling agent. The coating prepared by the coating has the advantages of good transparency, wear resistance, high adhesive force, ultraviolet aging resistance, boiling resistance, high and low temperature impact resistance, humidity and heat resistance, salt mist resistance and the like; the compactness of the coating is improved by improving the crosslinking density of the coating, and the adhesive force performance of the coating after water boiling is met; a flexible chain segment with good rotation property is introduced into a coating system, so that the flexibility of the coating is improved, the crack resistance is improved, and the adhesive force of the coating is further improved.
Description
Technical Field
The invention relates to the technical field of coating coatings, in particular to a boiling-resistant coating, a coating, and a preparation method and application thereof.
Background
Compared with the traditional inorganic glass, the organic glass is widely applied due to the advantages of good toughness, high strength, easy processing and forming and the like, wherein the polycarbonate transparent material is widely applied to various fields, but due to the defects of the organic glass, a corresponding coating matched with the organic glass is required to meet the application requirements of the material, the matched coating needs to have the requirements of high light transmittance, good wear resistance, high adhesive force, ultraviolet irradiation resistance and the like, at present, a great deal of research is carried out by researchers at home and abroad aiming at the performances of the coating, for example, in the American patent US3986997, colloidal silica and methyltriethoxysilane are adopted as raw materials to prepare the transparent hardening coating. USP4291098 adopts epoxy resin as an adhesion promoter to prepare the primer-free wear-resistant high-adhesion coating. Chinese patent ZL2017100034919 adopts methyl triethoxysilane modified silica sol and introduces an ultraviolet absorbent to prepare the wear-resistant and ultraviolet-resistant coating. With the application of more and more functions of transparent materials, higher requirements are correspondingly put on a coating matched with the transparent materials, for example, in high and low temperature alternation, high temperature and high humidity environment and ocean salt mist environment, the coating often cracks and even peels off from a substrate.
At present, most of researches on coatings focus on the researches on the transparency, wear resistance, adhesion and ultraviolet resistance of the coatings in conventional environments, but the adhesion and cracking problems of the coatings are not researched too much during the use process of the coatings or after some harsh environmental tests (such as high temperature and high humidity, high and low temperature alternation, salt fog environment and the like).
Disclosure of Invention
The invention aims to provide a boiling-resistant coating, a preparation method and application aiming at the problems of insufficient adhesive force and cracking of the existing coating in the using process or in some harsh environment tests, wherein the coating formed by coating the coating on the surface of polycarbonate has the characteristics of wear resistance, boiling resistance, high and low temperature impact resistance, humidity and heat resistance and salt mist resistance; a flexible chain segment with good rotation property is introduced into a coating system, so that the flexibility of the coating is improved, the crack resistance is improved, and the adhesive force of the coating is further improved.
In order to achieve the purpose, the invention adopts the technical scheme that the boiling-resistant coating comprises the following components in percentage by weight: 25-55% of alkoxy silane with at least three functionalities, 5-20% of alkaline silica sol, 5-10% of distilled water, 0.3-3% of acetic acid, 78-20% of solvent A10, 3-8% of flexible chain segment and 2-6% of silane coupling agent, wherein the sum of the weight percentages of the above components is one hundred percent.
Preferably, the alkoxysilane with at least three functionalities is at least one selected from the group consisting of methyltriethoxysilane, methyltrimethoxysilane, tetraethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, dodecyltriethoxysilane, and dodecafluoroheptylpropyltrimethoxysilane.
Preferably, the alkaline silica sol is an aqueous silica sol having a solid content of 28%.
Preferably, the solvent a is at least one selected from ethanol, n-propanol, isopropanol, butanol, isobutanol, ethylene glycol butyl ether, propylene glycol methyl ether, and diacetone alcohol.
Preferably, the silane coupling agent is at least one selected from the group consisting of gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, 3- (methacryloyloxy) propylmethyldimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, and gamma- (methacryloyloxy) propyltriethoxysilane.
Preferably, the soft chain segment comprises the following components in percentage by weight: 30-45% of monomer containing two terminal-OH groups, 15-22% of monomer containing two terminal-NCO groups, 15-22% of alkoxy silane monomer containing NCO groups, 20-30% of solvent B and 0.01-0.05% of catalyst, wherein the sum of the weight percentages of the above components is one hundred percent;
further, the monomer containing two terminal-OH groups is at least one selected from 1-6 hexanediol, PPG800, PPG600, PH-90 and PH-200.
Further, the monomer containing two terminal-NCO groups is at least one selected from the group consisting of Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), and diphenylmethane diisocyanate (MDI).
Further, the alkoxy silane monomer containing NCO group is selected from at least one of 3-isocyanate group propyl triethoxy silane, 3-isocyanate group propyl methyl dimethoxy silane, 3-isocyanate group propyl methyl diethoxy silane and 3-isocyanate group propyl trimethoxy silane.
Further, the solvent B is at least one selected from butyl acetate, ethyl acetate, xylene, tetrahydrofuran, 2-butoxyethyl acetate, diacetone alcohol and DBE.
Further, the catalyst is at least one selected from dibutyltin dilaurate, dibutyltin diacetate and stannous octoate.
Further, the preparation method of the flexible chain segment comprises the steps of mixing a monomer containing two terminal-OH groups and a monomer containing two terminal-NCO groups, adding the mixture into a three-necked bottle, adding a catalyst, reacting for 12 hours at 50-60 ℃ under heat preservation, then dropwise adding an alkoxy silane monomer containing NCO groups under heat preservation, continuing reacting for 8 hours under heat preservation after 1-2 hours of dropwise adding is finished, adding a solvent B, and stirring for 0.5 hour to obtain the flexible chain segment.
The invention also provides a preparation method of the boiling-resistant coating, which comprises the steps of adding alkaline silica sol and distilled water into a reactor for priming, adding hydrochloric acid for adjusting pH, adding alkoxy silane with at least three functionalities and a flexible chain segment, continuously stirring for reaction for 0.5-1 h, adding a solvent and a silane coupling agent, heating for reflux reaction for 1-3 h, cooling, and stopping reaction to obtain a finished product.
The invention also provides a boil-resistant coating comprising: the coated anti-boiling coating.
The invention further provides a preparation method of the coating, and specifically the prepared coating is coated on the surface of a base material by a flow coating method, the surface drying time is 0.5-1 h, and then the coating is baked in a drying oven at 120 ℃ for 2h to obtain the boiling-resistant coating.
The invention also provides application of the boiling-resistant coating in the field of organic glass.
Compared with the prior art, the invention has the beneficial technical effects that: the coating prepared by the coating has the advantages of good transparency, wear resistance, high adhesive force, ultraviolet aging resistance, boiling resistance, high and low temperature impact resistance, humidity and heat resistance, salt mist resistance and the like; the compactness of the coating is improved by improving the crosslinking density of the coating, and the adhesive force performance of the coating after water boiling is met; a flexible chain segment with good rotation property is introduced into a coating system, so that the flexibility of the coating is improved, the crack resistance is improved, and the adhesive force of the coating is further improved.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description of the present invention is provided with reference to specific embodiments.
Example 1
Preparing a flexible chain segment: adding 50g of 1-6 hexanediol and 22g of Hexamethylene Diisocyanate (HDI) into a three-necked bottle, adding 0.05g of dibutyltin dilaurate into the three-necked bottle continuously, carrying out heat preservation reaction at 50 ℃ for 12 hours, then carrying out heat preservation, dropwise adding 25g of 3-isocyanatopropyltriethoxysilane into the three-necked bottle, continuing to carry out heat preservation reaction for 8 hours after dropwise adding is finished for 1-2 hours, then adding 33g of xylene, and carrying out stirring reaction for 0.5 hour to obtain R1.
Preparation of the boiling-resistant coating: adding 25g of alkaline silica sol and 15g of distilled water into a reactor for priming, adding 4g of acetic acid for adjusting the pH value, adding 70g of methyltriethoxysilane, 30g of tetraethoxysilane and 5gR1, continuously stirring for reaction for 0.5-1 h, adding 45g of isopropanol and 12g of gamma-glycidyl ether oxypropyl trimethoxysilane, heating for reflux reaction for 1-3 h, and cooling to stop the reaction to obtain the boiling-resistant coating A.
Example 2
The soft segment was prepared in the same manner as in example 1 to obtain R1.
Preparation of the boiling-resistant coating: adding 32g of alkaline silica sol and 17g of distilled water into a reactor for priming, adding 4g of acetic acid for adjusting the pH value, adding 70g of methyltriethoxysilane, 20g of tetraethoxysilane, 15g of dodecafluoroheptyl propyl trimethoxy silane and 7gR1, continuously stirring for reacting for 0.5-1 h, adding 50g of diacetone alcohol and 15g of gamma-glycidyl ether oxypropyl trimethoxy silane, heating for reflux reacting for 1-3 h, and cooling to stop the reaction to obtain the coating B.
Example 3
Preparing a flexible chain segment: adding 66g of PPG800 and 27g of dicyclohexylmethane diisocyanate (HMDI) into a three-necked flask, adding 0.05g of dibutyltin dilaurate into the three-necked flask continuously, carrying out heat preservation reaction at 50-60 ℃ for 12h, then carrying out heat preservation dropwise adding 25g of 3-isocyanatopropyltriethoxysilane, continuing to carry out heat preservation reaction for 8h after 1-2 h of dropwise adding is finished, then adding 35g of acetic acid (2-butoxyethyl) ester, and carrying out stirring reaction for 0.5h to obtain R2.
Preparation of the boiling-resistant coating: adding 20g of alkaline silica sol and 15g of distilled water into a reactor for priming, adding 4g of acetic acid for adjusting the pH value, adding 80g of methyltriethoxysilane, 40g of tetraethoxysilane and 10gR2, continuously stirring for reaction for 0.5-1 h, adding 20g of diacetone alcohol, 20g of ethanol and 10g of gamma- (methacryloyloxy) propyltriethoxysilane, heating for reflux reaction for 1-3 h, and cooling to stop the reaction to obtain the coating C.
Example 4
The soft segment was prepared in the same manner as in example 3 to obtain R2.
Preparation of the boiling-resistant coating: adding 30g of alkaline silica sol and 17g of distilled water into a reactor for priming, adding 3g of acetic acid for adjusting the pH value, adding 90g of phenyltriethoxysilane, 30g of tetraethoxysilane and 15gR2, continuously stirring for reaction for 0.5-1 h, adding 20g of diacetone alcohol, 30g of isopropanol and 17g of gamma-glycidyl ether oxypropyl methyldimethoxysilane, heating for reflux reaction for 1-3 h, and cooling to stop the reaction to obtain the coating D.
Example 6
Preparing a flexible chain segment: r1 was obtained as in example 1 and R2 was obtained as in example 3 and was used.
Preparation of the boiling-resistant coating: adding 12g of alkaline silica sol and 20g of distilled water into a reactor for priming, adding 3g of acetic acid for adjusting the pH value, adding 80g of phenyltriethoxysilane, 40g of tetraethoxysilane, 5gR1 and 5gR2, continuously stirring for reaction for 0.5-1 h, adding 20g of diacetone alcohol, 20g of ethanol and 12g of gamma-glycidyl ether oxypropyl trimethoxysilane, heating for reflux reaction for 1-3 h, and cooling to stop the reaction to obtain the coating E.
Example 7
A boil-resistant coating, coated with any one of the boil-resistant coatings prepared in examples 1-6.
Example 8
Use of the poaching-resistant coating described in example 7 on polycarbonate glass surfaces. The boiling-resistant coating A, B, C, D, E of examples 1-6 is prepared into a coating on the surface of polycarbonate glass by a flow coating process to obtain a coating A, a coating B, a coating C, a coating D and a coating E, the surface drying time after coating is not less than 30min, and the coating is baked in an environment at 120 ℃ for not less than 120 min.
Test of
The polycarbonate glass surface coating of example 8 was tested for boil resistance, high and low temperature impact resistance, wet heat resistance, and salt spray resistance.
The boiling resistance test is to put the prepared sample plate into boiling distilled water, and the adhesive force of the coating is tested after 5 hours (cross-cut method); testing the adhesion of the coating after 20 cycles (cross-hatch method) by using the test standard of ASTM D3359 for high and low temperature impact; the wet heat resistance adopts the test standard of ASTM D3359, and the coating adhesion force is obtained after 20 periods (cross-hatch method); the salt spray resistance was measured using the test standard of ASTM D3359, the adhesion of the coating was measured after 96 hours (cross-hatch method), and the test results are shown in Table I.
Test of the Properties of the coating
| Coating A | Coating B | Coating C | Coating D | Coating E | |
| Resistant to boiling in water (adhesion, B) | 4 | 4 | 5 | 5 | 5 |
| High and Low temperature impact (adhesion, B) | 4 | 5 | 4 | 5 | 5 |
| Damp and heat resistance (adhesion, B) | 4 | 5 | 5 | 5 | 5 |
| Salt spray resistance (adhesion, B) | 4 | 4 | 5 | 5 | 5 |
The results show that: the coating A, B, C, D, E prepared by the embodiment of the invention has high boiling resistance, high and low temperature impact resistance, humidity and heat resistance and salt mist resistance, and the corresponding adhesive force reaches more than 4B.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (9)
1. The boiling-resistant coating comprises the following components in percentage by weight:
the sum of the weight percentages of the components is one hundred percent.
2. The poaching-resistant coating of claim 1, wherein: the flexible chain segment comprises the following components in percentage by weight:
the sum of the weight percentages of the components is one hundred percent.
3. The poaching-resistant coating of claim 2, wherein: the alkoxy silane with at least three functionalities is selected from at least one of methyl triethoxysilane, methyl trimethoxysilane, ethyl orthosilicate, phenyl triethoxysilane, phenyl trimethoxysilane, dodecyl triethoxysilane and dodecafluoroheptyl propyl trimethoxysilane; the alkaline silica sol is water-based silica sol, and the solid content of the alkaline silica sol is 28%; the solvent A is selected from at least one of ethanol, n-propanol, isopropanol, butanol, isobutanol, ethylene glycol butyl ether, propylene glycol methyl ether and diacetone alcohol; the silane coupling agent is selected from at least one of gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, 3- (methacryloyloxy) propylmethyldimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane and gamma- (methacryloyloxy) propyltriethoxysilane.
4. The poaching-resistant coating of claim 3, wherein: the monomer containing two terminal-OH groups is at least one selected from 1-6 hexanediol, PPG800, PPG600, PH-90 and PH-200; the monomer containing two terminal-NCO groups is at least one of Hexamethylene Diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI) and diphenylmethane diisocyanate (MDI); the alkoxy silane monomer containing NCO group is at least one selected from 3-isocyanate group propyl triethoxy silane, 3-isocyanate group propyl methyl dimethoxy silane, 3-isocyanate group propyl methyl diethoxy silane and 3-isocyanate group propyl trimethoxy silane; the solvent B is at least one selected from butyl acetate, ethyl acetate, xylene, tetrahydrofuran, 2-butoxyethyl acetate, diacetone alcohol and DBE; the catalyst is at least one of dibutyltin dilaurate, dibutyltin diacetate and stannous octoate.
5. The poaching-resistant coating of claim 2, wherein: the preparation method of the flexible chain segment comprises the steps of mixing a monomer containing two terminal-OH groups and a monomer containing two terminal-NCO groups, adding the mixture into a three-necked bottle, adding a catalyst, reacting for 12 hours at the temperature of 50-60 ℃, then dropwise adding an alkoxy silane monomer containing NCO groups in a heat preservation manner, continuing reacting for 8 hours in a heat preservation manner after 1-2 hours of dropwise adding, adding a solvent B, and stirring for 0.5 hour to obtain the flexible chain segment.
6. A method of preparing the boiling-resistant coating of claim 5, characterized in that: adding alkaline silica sol and distilled water into a reactor for priming, adding hydrochloric acid for adjusting pH, adding alkoxy silane with at least three functionalities and a flexible chain segment, continuously stirring for reaction for 0.5-1 h, adding a solvent and a silane coupling agent, heating for reflux reaction for 1-3 h, cooling, and stopping reaction to obtain a finished product.
7. A boiling-resistant coating, comprising: the coated, poaching-resistant coating of any one of claims 1-4.
8. A method of preparing a boil-resistant coating of claim 7, wherein: the prepared boiling-resistant coating is coated on the surface of a base material by adopting a flow coating method, the surface drying time is 0.5-1 h, and then the coating is baked in a drying oven at the temperature of 120 ℃ for 2h to obtain the boiling-resistant coating.
9. Use of a boiling-resistant coating as claimed in claim 7 in the field of organic glass.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111961407A (en) * | 2020-08-27 | 2020-11-20 | 厦门三德信科技股份有限公司 | Colorless polyimide explosion-proof layer and preparation method thereof |
| CN114163926A (en) * | 2021-12-20 | 2022-03-11 | 江苏三木化工股份有限公司 | Organic silicon resin for air-drying high-performance solar panel and fan blade paint and preparation method thereof |
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| CN106675396A (en) * | 2017-01-04 | 2017-05-17 | 中昊北方涂料工业研究设计院有限公司 | Wear resistance and anti-ultraviolet coating for polycarbonate and preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102015811A (en) * | 2008-04-25 | 2011-04-13 | 汉高公司 | Curable compositions containing silylated polyether block polymer-based polyurethanes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111961407A (en) * | 2020-08-27 | 2020-11-20 | 厦门三德信科技股份有限公司 | Colorless polyimide explosion-proof layer and preparation method thereof |
| CN114163926A (en) * | 2021-12-20 | 2022-03-11 | 江苏三木化工股份有限公司 | Organic silicon resin for air-drying high-performance solar panel and fan blade paint and preparation method thereof |
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Application publication date: 20200331 |