CN112500808A - Antibacterial paint surface protective film - Google Patents
Antibacterial paint surface protective film Download PDFInfo
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- CN112500808A CN112500808A CN202011401126.1A CN202011401126A CN112500808A CN 112500808 A CN112500808 A CN 112500808A CN 202011401126 A CN202011401126 A CN 202011401126A CN 112500808 A CN112500808 A CN 112500808A
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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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
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2427/00—Presence of halogenated polymer
- C09J2427/006—Presence of halogenated polymer in the substrate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
- C09J2433/006—Presence of (meth)acrylic polymer in the substrate
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
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Abstract
The invention relates to the technical field of paint surface protective films, in particular to an antibacterial paint surface protective film which comprises a transparent supporting body, wherein a self-repairing antibacterial protective layer and a transparent release film are sequentially arranged on one optical surface of the transparent supporting body; and assembling glue and a semitransparent release film are sequentially arranged on the other optical surface of the transparent support body. The self-repairing type antibacterial protective layer is formed by coating a self-repairing type antibacterial coating liquid and then heating and curing the coating liquid, the self-repairing type antibacterial coating liquid protects self-repairing main body resin, the self-repairing main body resin is formed by mixing two kinds of resins with a hydroxyl value range of 120 mgKOH/g-140 mgKOH/g and a hydroxyl value range of 50 mgKOH/g-70 mgKOH/g, and the mixing ratio is (7-9): (1-3). Can effectively resist escherichia coli and staphylococcus aureus, and the self-repairing layer has good permeation resistance.
Description
Technical Field
The invention relates to the technical field of paint surface protective films, in particular to an antibacterial paint surface protective film.
Background
The paint surface protective film is a layer of transparent protective film which is stuck on paint on the surface of a product, is mainly used in industries such as automobile cosmetology in the automobile aftermarket at present, and can achieve the effect of protecting original factory automobile paint of an automobile from being damaged by external force; and can also be used for the parts needing to be adhered with the protective film, such as building material surface decoration, street lamps, guardrails, metal handles and the like. This product has very strong toughness, still has self-repairing function, can effectually prevent to scrape and rub the hitting of gravel, has still completely cut off the contact of lacquer painting and air, can prevent the injury to the product lacquer painting such as acid rain, pitch, bird droppings. Meanwhile, the paint surface protective film has high definition and high brightness, and can improve and protect the color and the glossiness of the paint surface of a product.
With the increasing variety of epidemic diseases in recent years, the antibacterial performance is required on the surface of products, and although the space network structure of the paint protective film self-repairing layer provides excellent self-repairing function, the surface of the paint protective film self-repairing layer is easy to permeate by small molecules, so that the space network can absorb and contain microorganisms. In order to give consideration to the self-repairing performance and the surface permeation resistance of the paint protective film, further improve the antibacterial performance of the paint protective film, effectively reduce the survival time of germs and microorganisms on the surface of the paint protective film, a proper antibacterial self-repairing formula and a production method are urgently needed to be found, and a paint protective film product with an antibacterial function is made.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art, and provides an antibacterial paint surface protective film which can effectively resist escherichia coli and staphylococcus aureus and has a good permeation resistance of a self-repairing layer.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: an antibacterial paint surface protective film comprises a transparent support body, wherein a self-repairing antibacterial protective layer and a transparent release film are sequentially arranged on one optical surface of the transparent support body; the other optical surface of the transparent support body is sequentially provided with an assembly adhesive and a semitransparent release film, the self-repairing type antibacterial protective layer is formed by coating a self-repairing type antibacterial coating liquid and then heating and curing, and the self-repairing type antibacterial coating liquid comprises the following components in parts by weight:
the self-repairing main body resin is formed by mixing two kinds of resins with a hydroxyl value range of 120 mgKOH/g-140 mgKOH/g and a hydroxyl value range of 50 mgKOH/g-70 mgKOH/g, and the mixing ratio is (7-9): (1-3).
As an improved technical scheme of the application, the metal antibacterial agent comprises a silver ion antibacterial agent and a zinc ion antibacterial agent, and the mixing ratio of the silver ion antibacterial agent to the zinc ion antibacterial agent is (7-8): (2-3).
As an improved technical scheme of the application, the curing agent comprises one of aliphatic isocyanate and alicyclic isocyanate or two of the aliphatic isocyanate and the alicyclic isocyanate in any weight ratio.
As an improved technical scheme of the application, the metal catalyst is one of an organic tin catalyst, an organic bismuth catalyst or a rare earth catalyst.
According to the technical scheme, when the paint surface protective film is prepared, a metal antibacterial agent is uniformly dispersed in resin with a high hydroxyl value, then an organic solvent, a leveling aid and a catalyst in a proportioning amount are added, the resin with a low hydroxyl value diluted in advance is slowly added after uniform mixing, finally a curing agent is added and uniformly mixed to obtain an antibacterial self-repairing layer coating liquid, the coating liquid is fully defoamed and then coated on a supporting body, a release protective film is attached after drying at the temperature of 100-140 ℃, and then the coating liquid is cured for 60-96 hours at the temperature of 45-80 ℃ to obtain the antibacterial paint surface protective film product.
As an improved technical scheme of the application, the thickness of the self-repairing antibacterial protective layer is 5-30 microns.
As an improved technical scheme of the application, the transparent support is a polyvinyl chloride film, a thermoplastic polyurethane film, a PET film, a PMMA film or a TAC film; the thickness of the transparent support is 50-300 μm.
As an improved technical scheme of the application, the organic solvent is one or more of butanone, toluene, methyl isobutyl ketone, ethyl acetate, butyl acetate and propylene glycol methyl ether in any weight ratio.
Compared with the prior art, the method has the advantages that,
1. the main resin of the self-repairing layer is formed by mixing two kinds of resin with the hydroxyl value range of 120 mgKOH/g-140 mgKOH/g and the hydroxyl value range of 50 mgKOH/g-70 mgKOH/g, wherein the high-hydroxyl-value resin has more reactive groups, the cross-linking density of the system is improved, a good space network structure of the self-repairing layer is provided, the low-hydroxyl-value resin has good thermoplastic performance of the system, and the two kinds of main resin are matched in a specific proportion for use, so that the self-repairing paint surface protective film has excellent tensile property and self-repairing property.
2. According to the invention, the silver-zinc mixed antibacterial agent is added, so that the self-repairing coating has good antibacterial and mildew-proof properties, and after the antibacterial agent is added, the metal antibacterial agent fills part of space grid gaps, so that the color penetration resistance of the coating is obviously superior to that before the addition, and the reflection brightening effect is obviously improved.
3. When the antibacterial self-repairing coating liquid is prepared, the antibacterial agent and the high-hydroxyl-value resin with high crosslinking density are premixed, the solvent and the catalyst are added, so that the metal antibacterial agent is crosslinked on the high-hydroxyl-value resin and can be uniformly distributed in the space network structure, and the low-hydroxyl-value resin and the curing agent are added, so that the long-acting antibacterial effect is achieved after the film is formed.
Detailed Description
In order to make the purpose and technical solution of the embodiments of the present invention clearer, the technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
In the invention, the metal antibacterial agent is mainly a silver ion antibacterial agent and a zinc ion antibacterial agent. The silver ion antibacterial agent has excellent heat resistance and broad-spectrum performance and higher safety, but silver is easy to oxidize and discolor, so the zinc ion antibacterial agent and the silver ion antibacterial agent are matched for use, so that the silver ion antibacterial agent not only can play a good role in synergistic antibacterial action, but also can improve the problem of easy discoloration caused by the independent use of silver ions to a certain extent. The mixing ratio of the silver ion antibacterial agent and the zinc ion antibacterial agent in the invention is preferably (7-8): (2-3).
The addition proportion of the metal antibacterial agent is 0.5-3 parts by weight, when the addition amount is less than 0.5 part by weight, an obvious antibacterial effect cannot be achieved, and when the addition amount exceeds 3 parts by weight, the apparent performance of the self-repairing coating is influenced. The silver ion antibacterial agent comprises: shanghai Jingan industry Co., Ltd. (10000PPM concentration, particle size distribution 5-7nm), Langyi New antibacterial silver ion antibacterial agent, Guangzhou Ahaole mildew-proof antibacterial science Co., Ltd.: iHeir-PSZ104 silver ion antibacterial agent, Dongguan Sheng chemical industry Co., Ltd., (Guangzhou Shenyue trade Co., Ltd.) (Yangye trade Co., Ltd.), silver ion antibacterial agent Asjia S + AM001-ZA (Guangzhou Shenyue trade Co., Ltd.), Ringtai Sanitized silver ion antibacterial agent BCA21-61 (Guangzhou Shenyue trade Co., Ltd.), Nijiyue Mei Zeomic antibacterial agent-silver ion antibacterial agent, Japanese silver ion antibacterial agent IONPURE ZAF (Guangzhouyue trade Co., Ltd.). The zinc ion antibacterial agent comprises: high-concentration nano zinc solution (150000PPM concentration, 3-5nm particle size distribution) of Shanghai Jing Anhui Co., Ltd, Lanyi New Material AntibacMax zinc ion antibacterial agent, Dongguan Yisheng chemical Co., Ltd zinc ion antibacterial agent, zinc ion antibacterial agent Asjia S + AM001-ZN (Guangzhou Shenyue trade Co., Ltd) Nanjing Tianshi Landun Biotech Co., Ltd.
In the invention, the self-repairing main body resin accounts for 20-60 parts by weight, and is formed by mixing two resins with a hydroxyl value range of 120-140 mgKOH/g and a hydroxyl value range of 50-70 mgKOH/g, wherein the mixing ratio is (7-9): (1-3). The high hydroxyl resin has more reactive groups, can improve the crosslinking density of a system, provides a good space network structure of a self-repairing layer, the low hydroxyl resin provides a good thermoplastic performance of the system, and the two main resins are matched in a specific ratio for use, so that the self-repairing paint surface protective film has excellent tensile property and self-repairing property.
In the present invention, the curing agent is isocyanate. Isocyanate is a generic name for various esters of isocyanic acid and is an important raw material for the synthesis of polyurethane resins. Isocyanates are classified by chemical structure into aromatic isocyanates, aliphatic isocyanates, alicyclic isocyanates, and other isocyanates. In order to ensure that the protective layer has lasting protection, yellowing resistance and acid and alkali resistance, the invention selects aliphatic isocyanate, alicyclic isocyanate or a composition of the aliphatic isocyanate and the alicyclic isocyanate in any weight ratio. Specific isocyanates are commercially available: hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, xylylene diisocyanate, tetramethylm-xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, cyclohexanedimethylene diisocyanate, methylcyclohexyl diisocyanate. The amount of the curing agent added is preferably 8 to 24 parts by weight in order to achieve an excellent antifouling effect of the protective layer.
In the present invention, a metal catalyst is added in order to increase the curing speed of the protective layer. The catalyst is a substance capable of accelerating oxidation and polymerization of paint to dry a film, and is generally classified into a tertiary amine catalyst and a metal catalyst. In order to ensure that the protective layer can be dried quickly and achieve good protection and antifouling effects, any one of an organic tin catalyst, an organic bismuth catalyst and a rare earth catalyst is preferably selected. Exemplary metal catalysts are: german chemical DY-12, American atmospheric chemical T-12, triton chemical T-20, Kasol auxiliary B1610, Kasol auxiliary B-18 and the like. The amount of addition is preferably 0.2 to 0.8 part by weight.
If necessary, 20 to 70 parts by weight of an organic solvent is further added to the protective coating liquid of the present invention. As long as the protective layer of the present invention can be formed on the support, a conventional organic solvent may be used without any limitation, for example: aliphatic hydrocarbons such as hexane, heptane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and dichloroethane; alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone, butanone, methyl isobutyl ketone, 2-pentanone and isophorone; esters such as ethyl acetate and butyl acetate; and cellosolve-based solvents such as ethyl cellosolve. Toluene, methyl isobutyl ketone, ethyl acetate, butyl acetate are preferred. The organic solvent may be used alone or in combination of two or more.
The leveling assistant is 0.5-10 parts by weight. BYK-431 (BYK chemical) can be selected; BYK-3570, Pico chemical; BYK-335, Pico chemical; silok-354, Stocko, et al.
In order to meet the requirement of high tensile property of the surface protective film of the automobile, the transparent support is a polyvinyl chloride film or a thermoplastic polyurethane film, and the thickness of the transparent support ranges from 50 micrometers to 300 micrometers.
The assembly glue is coated on a transparent support body, the coating thickness is preferably 10-50 μm, and the assembly glue is commercially available polyurethane or polyacrylate pressure-sensitive glue.
In the present invention, the protective layer is preferably applied by a slit coating method, a comma knife method, or a micro gravure coating method. When the paint surface protective film is prepared, firstly, a metal antibacterial agent is uniformly dispersed in resin with a high hydroxyl value, then, an organic solvent, a leveling auxiliary agent and a metal catalyst are added, after uniform mixing, resin with a low hydroxyl value which is diluted in advance is slowly added, finally, a curing agent is added, and uniform mixing is carried out to obtain an antibacterial self-repairing layer coating liquid.
Example 1
(1) Preparing a self-repairing antibacterial protective layer coating liquid:
42 parts by weight of a high hydroxyl value self-repairing main resin [ JZ-9540-10, hydroxyl value 130mgKOH/g, Jiazhi Xinnuo chemical industry ], 2.4 parts by weight of a metallic silver ion antibacterial agent [ particle size distribution 5-7nm, high concentration nano silver solution of Shanghai Jing 'an Engineer Co., Ltd ], 0.6 part by weight of a metallic zinc ion antibacterial agent [ particle size distribution 3-5nm, high concentration nano zinc solution of Shanghai Jing' an Engineer Co., Ltd ], stirring for 30 minutes, after the metallic antibacterial agent is uniformly dispersed in the resin, adding 12 parts by weight of a butyl acetate solvent, 3.8 parts by weight of a leveling aid [ BYK-431, Pico chemical ] and 0.2 parts by weight of a catalyst [ organotin catalyst-12, Dynol chemical ], stirring at a high speed for 30 minutes, slowly adding 18 parts by weight of a low hydroxyl value resin [ YP 0 2050SH diluted with 8 parts by weight of toluene after uniform mixing, hydroxyl value of 50mgKOH/g, Shanghai Yuanbang chemical industry Co., Ltd ], finally 13 parts by weight of a curing agent [ hexamethylene diisocyanate, Asahi chemical Co., Ltd ] was added, the mixture was stirred at a low speed for 30 minutes, and after mixing uniformly, the mixture was left to stand for defoaming for 90 minutes to obtain an antibacterial self-repairing layer coating liquid.
(2) Preparing a paint protective film:
coating transparent assembly glue on one surface of a thermoplastic polyurethane film support body with the thickness of 150 mu m and attaching a semitransparent release film; coating the prepared antibacterial self-repairing coating liquid on the other surface of the support body in a strip-and-slit coating mode, drying and curing for 5min at 100 ℃/120 ℃/140 ℃/120 ℃/100 ℃ in a stepped heating mode to obtain an antibacterial self-repairing protective layer with the thickness of 30 mu m, and then coating a transparent release film on the protective layer. Finally, putting the mixture into a curing chamber at the temperature of 80 ℃ for curing for 60 hours to obtain the paint surface protective film. The protective layer was tested for performance and the results are shown in table 1.
Example 2
(1) Preparing a self-repairing antibacterial protective layer coating liquid:
36 parts by weight of high hydroxyl value self-repairing main body resin [ PU-361, hydroxyl value 120mgKOH/g, Jieshida fine chemical Co., Ltd., Zhongshan city ], 1.4 parts by weight of metallic silver ion antibacterial agent [ Langmui, AntibacMax ], 0.6 part by weight of metallic zinc ion antibacterial agent [ Langmui, AntibacMax ], stirring for 30 minutes, after the metallic antibacterial agent is dispersed evenly in the resin, adding 29.6 parts by weight of ethyl acetate solvent, 10 parts by weight of leveling assistant [ BYK-3570, Pico ] and 0.4 part by weight of catalyst [ T-12, American air chemistry ], stirring for 30 minutes at high speed, mixing evenly, then slowly adding 4 parts by weight of low hydroxyl value resin [ YP31-7EXS, hydroxyl value 70mgKOH/g, Shanghai Yuanbang manufacturing Co, Ltd ], finally adding 8 parts by weight of curing agent [ dicyclohexylmethane-4%, 4' -diisocyanate, Wanhua ], stirring at a low speed for 30min, uniformly mixing, standing for defoaming for 90 min, and obtaining the antibacterial self-repairing layer coating liquid.
(2) Preparing a paint protective film:
coating transparent assembly glue on one side of a polyvinyl chloride film support body with the thickness of 225 mu m and attaching a semitransparent release film; and coating the prepared antibacterial self-repairing coating liquid on the other side of the support body in a comma roller coating mode, drying and curing at 120 ℃ for 5min to obtain an antibacterial self-repairing protective layer with the thickness of 24 mu m, and then coating a transparent release film on the protective layer. Finally, putting the mixture into a curing chamber at 60 ℃ for curing for 96h to obtain the paint surface protective film. The protective layer was tested for performance and the results are shown in table 1.
Example 3
(1) Preparing a self-repairing antibacterial protective layer coating liquid:
28.8 parts by weight of high hydroxyl value self-repairing main body resin [ DIANAL LR-7568, hydroxyl value 140mgKOH/g, Mitsubishi positive polymer material Co., Ltd ], 0.4 parts by weight of metallic silver ion antibacterial agent [ Zeomic silver ion antibacterial agent, Nijie and Mei ], 0.1 parts by weight of metallic zinc ion antibacterial agent [ Zeomic zinc ion antibacterial agent, Nijie and Mei ], stirring for 30 minutes, after the metallic antibacterial agent is uniformly dispersed in the resin, adding 20.5 parts by weight of propylene glycol methyl ether solvent, 4.4 parts by weight of leveling assistant [ BYK-335, Picko chemical ], and 0.6 parts by weight of catalyst [ rare earth catalyst B-18, CaoUX assistant ], stirring at high speed for 30 minutes, after uniform mixing, slowly adding 7.2 parts by weight of low hydroxyl value resin [ NAL-7506, hydroxyl value 66 KOH/g diluted with 14 parts by weight of butyl acetate, mitsubishi yang polymer materials Co., Ltd.), finally 24 parts by weight of a curing agent [ xylylene diisocyanate, mol ] was added, and stirred at a low speed for 30 minutes, and after being mixed uniformly, the mixture was left to stand for defoaming for 90 minutes, to obtain an antibacterial self-repairing layer coating liquid.
(2) Preparing a paint protective film:
coating transparent assembly glue on one side of a local polyethylene glycol terephthalate film support body with the thickness of 125 mu m and attaching a semitransparent release film; and coating the prepared antibacterial self-repairing coating liquid on the other surface of the support body in a micro gravure roll coating mode, drying and curing at 130 ℃ for 3min to obtain an antibacterial self-repairing protective layer with the thickness of 17 mu m, and then coating a transparent release film on the protective layer. Finally, putting the mixture into a curing chamber at 60 ℃ for curing for 72h to obtain the paint surface protective film. The protective layer was tested for performance and the results are shown in table 1.
Example 4
(1) Preparing a self-repairing antibacterial protective layer coating liquid:
adding 16.5 weight parts of high hydroxyl value self-repairing main body resin [ HS3302, hydroxyl value 140mgKOH/g, Shanghai Haoyang industry development Limited ], 0.8 weight parts of metal silver ion antibacterial agent [ Japanese silver ion antibacterial agent IONPURE ZAF, Guangzhou Shenyue trade Limited ], 0.3 weight parts of metal zinc ion antibacterial agent [ Asjia S + AM001-ZN, Guangzhou Shenyue trade Limited ], stirring for 30 minutes, after the metal antibacterial agent is dispersed evenly in the resin, adding 30 weight parts of toluene solvent, 0.9 weight parts of leveling assistant [ Silok-354, skyco ] and 0.8 weight parts of catalyst [ T-20, triton chemistry ], stirring for 30 minutes at high speed, slowly adding 3.5 weight parts of low hydroxyl value resin [ DIANAL-7664, hydroxyl value 66mgKOH/g diluted by 40 weight parts of butyl acetate after even mixing, mitsubishi yang polymer materials Co., Ltd.), finally 8 parts by weight of a curing agent [ dicyclohexylmethane-4, 4' -diisocyanate, Wanhua ] was added, stirred at a low speed for 30min, mixed uniformly and then kept stand for defoaming for 90 min to obtain an antibacterial self-repairing layer coating liquid.
(2) Preparing a paint protective film:
coating transparent assembly glue on one surface of a PMMA film support body with the thickness of 50 mu m and attaching a semitransparent release film; and coating the prepared antibacterial self-repairing coating liquid on the other surface of the support body in a micro gravure roll coating mode, drying and curing at 100 ℃ for 3min to obtain an antibacterial self-repairing protective layer with the thickness of 5 microns, and then coating a transparent release film on the protective layer. Finally, putting the mixture into a curing chamber at 45 ℃ for curing for 60 hours to obtain the paint surface protective film. The protective layer was tested for performance and the results are shown in table 1.
Example 5
(1) Preparing a self-repairing antibacterial protective layer coating liquid:
37 weight portions of high hydroxyl value self-repairing main body resin (343 SR, hydroxyl value 120mgKOH/g, three specialty chemicals), 1.2 weight portions of metal silver ion antibacterial agent (Sanitized silver ion antibacterial agent BCA21-61, Guangzhou Shenyue trade company, etc.), 0.5 weight portions of metal zinc ion antibacterial agent (Nanjing Tianshi blue shield biotechnology company, etc.), stirring for 30 minutes, after the metal antibacterial agent is dispersed evenly in the resin, adding 16 weight portions of ethyl acetate solvent, 0.5 weight portions of leveling assistant (TECH-225, Tiger assistant) and 0.3 weight portions of catalyst (T-12, American air chemistry), stirring for 30 minutes at high speed, after even mixing, slowly adding 15 weight portions of low hydroxyl value resin (PU-332, hydroxyl value 63mgKOH/g, Zhongshan Jejie chemical industry Co., Ltd.), and finally, adding 19 parts by weight of a curing agent [ isophorone diisocyanate, winning creation ], stirring at a low speed for 30min, uniformly mixing, standing and defoaming for 90 min to obtain the antibacterial self-repairing layer coating liquid.
(2) Preparing a paint protective film:
coating transparent assembly glue on one surface of a polyvinyl chloride film support body with the thickness of 300 mu m and attaching a semitransparent release film; and coating the prepared antibacterial self-repairing coating liquid on the other side of the support body in a comma roller coating mode, drying and curing at 130 ℃ for 5min to obtain an antibacterial self-repairing protective layer with the thickness of 12 microns, and then coating a transparent release film on the protective layer. Finally, putting the mixture into a curing chamber at 70 ℃ for curing for 72h to obtain the paint surface protective film. The protective layer was tested for performance and the results are shown in table 1.
Comparative example 1
(1) Preparing a self-repairing antibacterial protective layer coating liquid:
36 parts by weight of high hydroxyl value self-repairing main body resin [ PU-361, hydroxyl value 120mgKOH/g, Jieshida fine chemical Co., Ltd., Zhongshan city ], 0.2 parts by weight of metallic silver ion antibacterial agent [ Langshi New Material, AntibacMax ], 0.2 parts by weight of metallic zinc ion antibacterial agent [ Langshi New Material, AntibacMax ], stirring for 30 minutes, after the metallic antibacterial agent is dispersed evenly in the resin, adding 29.6 parts by weight of ethyl acetate solvent, 10 parts by weight of leveling assistant [ BYK-337, Pico chemical ] and 0.4 parts by weight of catalyst [ T-12, American air chemistry ], stirring for 30 minutes at high speed, slowly adding 4 parts by weight of low hydroxyl value resin [ YP31-7EXS, hydroxyl value 70mgKOH/g, Shanghai Ningyuan manufacturing Co., Ltd ], finally adding 8 parts by weight of dicyclohexylmethane-4 parts by weight of curing agent, 4' -diisocyanate, Wanhua ], stirring at a low speed for 30min, uniformly mixing, standing for defoaming for 90 min, and obtaining the antibacterial self-repairing layer coating liquid.
(2) Preparing a paint protective film:
coating transparent assembly glue on one side of a polyvinyl chloride film support body with the thickness of 225 mu m and attaching a semitransparent release film; and coating the prepared antibacterial self-repairing coating liquid on the other side of the support body in a comma roller coating mode, drying and curing at 120 ℃ for 5min to obtain an antibacterial self-repairing protective layer with the thickness of 24 mu m, and then coating a transparent release film on the protective layer. Finally, putting the mixture into a curing chamber at 60 ℃ for curing for 96h to obtain the paint surface protective film. The performance of the protective layer is tested, the antibacterial property test is unqualified, and the oil pen permeability is deteriorated, and specific results are shown in table 1.
Comparative example 2
(1) Preparing a self-repairing antibacterial protective layer coating liquid:
26 parts by weight of high hydroxyl value self-repairing main body resin (343 SR, hydroxyl value 120mgKOH/g, Tri-specific chemical), 1.2 parts by weight of metal silver ion antibacterial agent (Sanitized silver ion antibacterial agent BCA21-61, Guangzhou Shenyue trade Co., Ltd.), 0.5 part by weight of metal zinc ion antibacterial agent (Nanjing Tianshi Langua Biotech Co., Ltd.) were added into a container, stirred for 30 minutes, after the metal antibacterial agent was dispersed uniformly in the resin, 16 parts by weight of ethyl acetate solvent, 0.5 part by weight of leveling aid (TECH-225, Tiger aid) and 0.3 part by weight of catalyst [ T-12, American air chemistry ] were added, stirred at high speed for 30 minutes, and after uniform mixing, 26 parts by weight of low hydroxyl value resin (PU-332, hydroxyl value 63mgKOH/g, Zhongshan Jed Jie chemical Co., Ltd.) was slowly added, 26 parts by weight of butyl acetate diluted with stirring, fine chemical industry Co., Ltd, and finally, adding 19 parts by weight of a curing agent [ isophorone diisocyanate, winning creation ], stirring at a low speed for 30min, uniformly mixing, standing and defoaming for 90 min to obtain the antibacterial self-repairing layer coating liquid.
(2) Preparing a paint protective film:
coating transparent assembly glue on one surface of a polyvinyl chloride film support body with the thickness of 300 mu m and attaching a semitransparent release film; and coating the prepared antibacterial self-repairing coating liquid on the other side of the support body in a comma roller coating mode, drying and curing at 130 ℃ for 5min to obtain an antibacterial self-repairing protective layer with the thickness of 12 microns, and then coating a transparent release film on the protective layer. Finally, putting the mixture into a curing chamber at 70 ℃ for curing for 72h to obtain the paint surface protective film. The performance, permeation resistance and self-repairing performance of the protective layer are tested to be poor, and specific results are shown in table 1.
Comparative example 3
(1) Preparing a self-repairing antibacterial protective layer coating liquid:
42 parts by weight of high hydroxyl value self-repairing main body resin [ JZ-9540-10, hydroxyl value 130mgKOH/g, Jiazhi Xinnuo chemical industry ], 15 parts by weight of butyl acetate solvent, 3.8 parts by weight of leveling assistant [ BYK-431, Pic chemical ] and 0.2 part by weight of catalyst [ organic tin catalyst DY-12, Dachon chemical), are added into a container, stirred at high speed for 30 minutes, and then slowly added with 18 parts by weight of low hydroxyl value resin [ YP2050SH, hydroxyl value 50mgKOH/g, Shanghai Yuanbang chemical industry Limited ] diluted with 8 parts by weight of toluene, finally added with 13 parts by weight of curing agent [ hexamethylene diisocyanate, Asahi chemical synthesis ], stirred at low speed for 30 minutes, and stirred uniformly and then kept stand for defoaming for 90 minutes to obtain the antibacterial self-repairing layer coating liquid.
(2) Preparing a paint protective film:
coating transparent assembly glue on one surface of a thermoplastic polyurethane film support body with the thickness of 150 mu m and attaching a semitransparent release film; coating the prepared antibacterial self-repairing coating liquid on the other surface of the support body in a strip-and-slit coating mode, drying and curing for 5min at 100 ℃/120 ℃/140 ℃/120 ℃/100 ℃ in a stepped heating mode to obtain an antibacterial self-repairing protective layer with the thickness of 30 mu m, and then coating a transparent release film on the protective layer. Finally, putting the mixture into a curing chamber at the temperature of 80 ℃ for curing for 60 hours to obtain the paint surface protective film. The test protective layer has no antibacterial performance, and the coating is not resistant to oil pen penetration, and the specific results are shown in table 1.
Table 1: performance test data sheet
The test methods for the properties in the table are as follows:
1. determination of self-healing Performance
And wiping the surface of the coating by using a special copper brush, scratching a plurality of scratches on the surface of the self-repairing coating under the condition of ensuring that the support body is not scratched, placing the test sample wafer in an environment at 60 ℃ for 5min, and taking out to check whether the scratches are repaired.
2. Determination of antibacterial Properties
Measured according to the method of standard JIS Z2801: 2010.
3. Determination of Pen resistance
And (3) marking a plurality of oil pen marks on the surface of the self-repairing coating by using an oil marking pen, wiping the self-repairing coating by using alcohol after the oil pen marks are naturally dried, checking the color permeation condition of the wiped film surface, and marking as excellent if the film surface is completely impermeable, marking as O if the film surface is slightly permeated, and marking as ● if the film surface is deeply permeated and cannot be wiped.
4. Determination of glossiness
Tested according to the method of standard ASTM D2457.
The above are merely embodiments of the present invention, which are described in detail and with particularity, and therefore should not be construed as limiting the scope of the invention. It should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the spirit of the present invention, and these changes and modifications are within the scope of the present invention.
Claims (8)
1. An antibacterial paint surface protective film comprises a transparent support body, wherein a self-repairing antibacterial protective layer and a transparent release film are sequentially arranged on one optical surface of the transparent support body; the self-repairing antibacterial protective layer is formed by coating a self-repairing antibacterial coating liquid and then heating and curing the coating liquid, and the self-repairing antibacterial coating liquid comprises the following components in parts by weight:
the self-repairing main body resin is formed by mixing two kinds of resins with a hydroxyl value range of 120 mgKOH/g-140 mgKOH/g and a hydroxyl value range of 50 mgKOH/g-70 mgKOH/g, and the mixing ratio is (7-9): (1-3).
2. The antibacterial paint surface protective film according to claim 1, wherein the metal antibacterial agent comprises a silver ion antibacterial agent and a zinc ion antibacterial agent, and the mixing ratio of the silver ion antibacterial agent to the zinc ion antibacterial agent is (7-8): (2-3).
3. The protective film according to claim 1, wherein the curing agent comprises one or two of aliphatic isocyanate and alicyclic isocyanate at any weight ratio.
4. The antibacterial paint surface protective film according to claim 1, wherein the metal catalyst is one of an organic tin catalyst, an organic bismuth catalyst or a rare earth catalyst.
5. The antibacterial paint surface protective film according to any one of claims 1 to 4, characterized in that when the paint surface protective film is prepared, the metal antibacterial agent is uniformly dispersed in the resin with a high hydroxyl value, the organic solvent, the leveling aid and the catalyst are added according to the proportion, the resin with a low hydroxyl value which is diluted in advance is slowly added after uniform mixing, the curing agent is added finally, the coating liquid of the antibacterial self-repairing layer is uniformly mixed to obtain the antibacterial coating liquid, the antibacterial coating liquid is fully defoamed and then coated on the supporting body, the release protective film is attached after drying at 100 to 140 ℃, and then the coating liquid is cured at 45 to 80 ℃ for 60 to 96 hours to obtain the antibacterial paint surface protective film product.
6. The protective film for paint surfaces as claimed in claim 5, wherein the thickness of the self-repairing antibacterial protective layer is 5 μm to 30 μm.
7. The antibacterial paint surface protective film according to claim 1, wherein the transparent support is a polyvinyl chloride film, a thermoplastic polyurethane film, a PET film, a PMMA film or a TAC film; the thickness of the transparent support is 50-300 μm.
8. The antibacterial paint surface protective film according to claim 1, wherein the organic solvent is one or more of butanone, toluene, methyl isobutyl ketone, ethyl acetate, butyl acetate and propylene glycol methyl ether in any weight ratio.
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