CN116102930A - Protective layer coating for cold stamping film and preparation method thereof - Google Patents
Protective layer coating for cold stamping film and preparation method thereof Download PDFInfo
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- CN116102930A CN116102930A CN202211711764.2A CN202211711764A CN116102930A CN 116102930 A CN116102930 A CN 116102930A CN 202211711764 A CN202211711764 A CN 202211711764A CN 116102930 A CN116102930 A CN 116102930A
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to the technical field of paint, in particular to protective layer paint for a cold-stamping film and a preparation method thereof, wherein the protective layer paint comprises the following raw materials in parts by weight: 1-5 parts of polytetrafluoroethylene, 20-40 parts of hydroxy acrylic resin, 10-20 parts of modified polyurethane resin, 1-5 parts of polyisocyanate, 1-3 parts of modified nano titanium dioxide, 1-3 parts of defoamer, 1-5 parts of cross-linking agent, 1-3 parts of dispersing agent and 20-40 parts of solvent. The protective layer coating has good adhesive property, impact strength, wear resistance, heat resistance and ageing resistance, and has the properties of lower glass transition temperature and viscosity, clear details, excellent upper ironing property and the like; the method for preparing the protective layer coating for the cold stamping film is simple and efficient, convenient to operate and control, high in quality of produced products, low in cost and convenient for industrial production.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a protective layer coating for a cold-stamping film and a preparation method thereof.
Background
With the increasing progress of technology and the continuous pursuit of environmental protection products and even environmental protection production, the cold stamping technology is paid more and more attention and development due to the unique advantages. The breakthroughs of cold stamping technology benefit from the high-tech technology of European and American industries, the existing cold stamping technology is different from the traditional gold stamping technology which relies on hot pressing to transfer electrochemical aluminum foils, the cold stamping technology is used for transferring electrochemical aluminum foils, the cold stamping technology is widely used in various printing industries nowadays, and the products after hot stamping have unique metallic luster which is different from the traditional gold stamping and have the effects of large area and small fineness. The cold stamping technology also avoids the pollution to the environment in the process of manufacturing the metal printing plate, and can save a large amount of energy sources in the printing process.
The cold stamping film consists of a base material, a release layer, a coloring layer, an aluminizing layer and a protective layer. In the hot stamping process, unlike the hot stamping process, the back surface of the film is coated with a glue layer, and the cold stamping technology is to directly coat a special UV cold stamping adhesive on the position of the printed matter to be decorated during printing. When the cold stamping film is contacted with the printed matter, the electric aluminum is transferred and adhered on the surface of the printed matter, which is coated with the adhesive and needs to be stamped, due to the solidification of the adhesive. In the gold stamping process, the protective layer plays a role in enhancing the combination force of the cold stamping film and the UV cold stamping adhesive, so that the adhesion fastness of gold stamping patterns is improved; on the other hand, the coating of the protective layer enables the cold stamping film to have lasting rolling storage stability.
Chinese patent CN104004476B discloses an adhesive for hot stamping of electric aluminum and a preparation method thereof, wherein the adhesive with good slitting property and strong adhesive force is obtained by adopting the effects of acrylate copolymer, silicon powder, rosin resin, petroleum resin and the like, but the prior art adds solid particles into a sizing material, and the obtained sizing material has poor powder solubility, rough film surface after solidification, wear resistance, heat resistance, ageing resistance and poor texture.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a protective layer coating for a cold stamping film, which has the advantages of good bonding property, impact strength, wear resistance, heat resistance, ageing resistance, low glass transition temperature, low viscosity, clear details, excellent hot stamping property and the like.
The invention further aims to provide a preparation method of the protective layer coating for the cold stamping film, which is simple and efficient, convenient to operate and control, high in quality of produced products, low in cost and convenient for industrial production.
The aim of the invention is achieved by the following technical scheme: the protective layer coating for the cold stamping film comprises the following raw materials in parts by weight: 1-5 parts of polytetrafluoroethylene, 20-40 parts of hydroxy acrylic resin, 10-20 parts of modified polyurethane resin, 1-5 parts of polyisocyanate, 1-3 parts of modified nano titanium dioxide, 1-3 parts of defoamer, 1-5 parts of cross-linking agent, 1-3 parts of dispersing agent and 20-40 parts of solvent.
Preferably, the material comprises the following raw materials in parts by weight: 1-5 parts of polytetrafluoroethylene, 20-30 parts of hydroxy acrylic resin, 10-20 parts of modified polyurethane resin, 1-5 parts of polyisocyanate, 1-3 parts of modified nano titanium dioxide, 1-3 parts of defoamer, 1-5 parts of cross-linking agent, 1-3 parts of dispersing agent and 20-40 parts of solvent.
The protective layer coating provided by the invention has good adhesive property, impact strength, wear resistance, heat resistance and ageing resistance, and has the properties of lower glass transition temperature, lower viscosity, clear details, excellent hot stamping property and the like. The coating prepared by blending polytetrafluoroethylene, hydroxy acrylic resin, modified polyurethane resin and the like reduces the surface tension of a coating system, so that the protective layer coating is easy to form a film; meanwhile, the addition of polytetrafluoroethylene reduces the impact strength of the whole coating system and improves the later hot stamping performance; hydroxyl in the hydroxyl acrylic resin reacts with polyisocyanate to crosslink, so that the strength of the coating is improved, meanwhile, the polyisocyanate introduces benzene ring rigid functional groups into the molecular chain of the coating, so that the acrylic resin with a weak crosslinked network structure is obtained, the glass transition temperature and the viscosity are low, and the strength of the protective layer is further improved; the modified nano titanium dioxide not only can improve the wear resistance, heat resistance and ageing resistance of the coating, but also can be filled in gaps of the polymer to further strengthen the polymer.
Preferably, the modified polyurethane resin comprises the following raw materials in parts by weight: 10-20 parts of polyester polyol, 1-3 parts of dihydroxypolydimethylsiloxane, 8-16 parts of 3- (triethoxysilyl) propyl isocyanate, 1-5 parts of chain extender and 0.5-1.0 part of initiator.
Preferably, the modified polyurethane resin is prepared by the steps of:
s1, adding polyester polyol, an initiator and dihydroxy polydimethylsiloxane into a reaction device according to parts by weight, uniformly mixing, heating to 30-50 ℃ for reaction to obtain silane grafted polyol for later use;
s2, adding the silane grafted polyol, 3- (triethoxysilyl) propyl isocyanate and a chain extender into a reaction device, uniformly mixing, heating to 40-60 ℃ and reacting to obtain the modified polyurethane resin.
The modified polyurethane resin is prepared by adopting the raw materials and the preparation method, and has good hardness and adhesion, water resistance, alcohol resistance and pollution resistance; and dihydroxy polydimethylsiloxane is introduced in the preparation process, and can generate a crosslinking reaction in the process of forming silanol by hydrolysis, so that the modified polyurethane resin with good adhesive force and good water resistance, alcohol resistance and stain resistance is obtained.
Preferably, the modified nano titanium dioxide is nano titanium dioxide treated by a coupling agent, and is prepared by the following method: 1-5 parts of silane coupling agent kh550 is dissolved in 40-80 parts of deionized water, 5-9 parts of nano titanium dioxide is added after uniform stirring, stirring is continued for 60-120min, heating is carried out to 60-70 ℃, and moisture is dried, so that the modified nano titanium dioxide is obtained.
The nano titanium dioxide improved by the method not only can improve the wear resistance, heat resistance and ageing resistance of the coating, but also can be filled in gaps of the polymer to further strengthen the polymer.
Preferably, the defoamer is a polyether modified silicone defoamer.
The foam generated by the dispersing agent can be eliminated by the added defoaming agent, so that the dispersing time is shortened; meanwhile, the bubble points in the coating can be eliminated by adding the defoaming agent, so that the coating is convenient to coat, and the coating film is more uniform.
Preferably, the crosslinking agent is a polycarbodiimide crosslinking agent.
Preferably, the dispersing agent is one or more of polycarboxylic acid polymer dispersing agent, phosphate type high molecular polymer dispersing agent and acrylate dispersing agent.
The coating system of the invention can uniformly disperse the rest raw materials in the slurry under the action of the dispersing agent.
Preferably, the solvent is one or more of ethyl acetate, n-propyl ester, cyclohexanone and butanone.
The invention also provides a preparation method of the protective layer coating for the cold stamping film, which comprises the following steps:
1) Adding the hydroxy acrylic resin, the modified polyurethane resin, the polyisocyanate and the modified nano titanium dioxide into a solvent according to parts by weight, uniformly stirring, and standing to obtain a mixed solution A for later use;
2) According to the weight portions, polytetrafluoroethylene, a defoaming agent, a cross-linking agent and a dispersing agent are mixed and then added into the mixed solution A, heated to 40-60 ℃ and stirred for 1-3h, and the protective layer coating is obtained.
The protective layer coating is prepared by the method, and the protective layer coating prepared by the method has good bonding performance, impact strength, wear resistance, heat resistance, ageing resistance, lower glass transition temperature and viscosity, clear details, excellent scalding performance and the like; the preparation method is simple and efficient, convenient to operate and control, high in quality of the produced product, low in cost and convenient for industrial production.
The invention has the beneficial effects that: the protective layer coating provided by the invention has good adhesive property, impact strength, wear resistance, heat resistance and ageing resistance, and has the properties of low glass transition temperature and viscosity, clear details, excellent hot stamping property and the like. The coating prepared by blending polytetrafluoroethylene, hydroxy acrylic resin, modified polyurethane resin and the like reduces the surface tension of a coating system, so that the protective layer coating is easy to form a film; meanwhile, the addition of polytetrafluoroethylene reduces the impact strength of the whole coating system and improves the later hot stamping performance; hydroxyl in the hydroxyl acrylic resin reacts with polyisocyanate to crosslink, so that the strength of the coating is improved, meanwhile, the polyisocyanate introduces benzene ring rigid functional groups into the molecular chain of the coating, so that the acrylic resin with a weak crosslinked network structure is obtained, the glass transition temperature and the viscosity are low, and the strength of the protective layer is further improved; the modified nano titanium dioxide not only can improve the wear resistance, heat resistance and ageing resistance of the coating, but also can be filled in gaps of the polymer to further strengthen the polymer.
The preparation method of the protective layer coating for the cold stamping film is simple and efficient, convenient to operate and control, high in quality of produced products, low in cost and convenient for industrial production.
Detailed Description
The invention will be further illustrated by the following examples, which are not intended to limit the scope of the invention, in order to facilitate the understanding of those skilled in the art.
Example 1
The protective layer coating for the cold stamping film comprises the following raw materials in parts by weight: 1 part of polytetrafluoroethylene, 20 parts of hydroxy acrylic resin, 10 parts of modified polyurethane resin, 1 part of polyisocyanate, 1 part of modified nano titanium dioxide, 1 part of defoamer, 1 part of cross-linking agent, 1 part of dispersing agent and 20 parts of solvent.
Wherein the modified polyurethane resin comprises the following raw materials in parts by weight: 10 parts of polyester polyol, 1 part of dihydroxypolydimethylsiloxane, 8 parts of 3- (triethoxysilyl) propyl isocyanate, 1 part of chain extender and 0.5 part of initiator.
Wherein the modified polyurethane resin is prepared by the following steps:
s1, adding polyester polyol, an initiator and dihydroxy polydimethylsiloxane into a reaction device according to parts by weight, uniformly mixing, heating to 30 ℃ for reaction to obtain silane grafted polyol for later use;
s2, adding the silane grafted polyol, 3- (triethoxysilyl) propyl isocyanate and a chain extender into a reaction device, uniformly mixing, heating to 40 ℃ and reacting to obtain the modified polyurethane resin.
Wherein, the modified nano titanium dioxide is prepared by the following method: 1 part of silane coupling agent kh550 is dissolved in 40 parts of deionized water, 5 parts of nano titanium dioxide is added after uniform stirring, stirring is continued for 60min, heating is carried out to 60 ℃, and moisture is dried, so that the modified nano titanium dioxide is obtained.
Wherein the defoamer is polyether modified organic silicon defoamer and F-1658 polyether modified silicon defoamer produced by Guangdong Tianfeng defoamer Co.
The cross-linking agent is polycarbodiimide cross-linking agent, which is supplied by Shanghai You En chemical company.
The dispersant is a polycarboxylic acid polymer dispersant.
The solvent is cyclohexanone.
The protective layer coating for the cold stamping film is prepared by the following steps:
1) Adding the hydroxy acrylic resin, the modified polyurethane resin, the polyisocyanate and the modified nano titanium dioxide into a solvent according to parts by weight, uniformly stirring, and standing to obtain a mixed solution A for later use;
2) And mixing polytetrafluoroethylene, a defoaming agent, a cross-linking agent and a dispersing agent according to parts by weight, adding the mixture into the mixed solution A, heating to 40 ℃, and stirring for 1h to obtain the protective layer coating.
Example 2
The protective layer coating for the cold stamping film comprises the following raw materials in parts by weight: 2 parts of polytetrafluoroethylene, 25 parts of hydroxy acrylic resin, 13 parts of modified polyurethane resin, 2 parts of polyisocyanate, 1.5 parts of modified nano titanium dioxide, 1.5 parts of defoamer, 2 parts of cross-linking agent, 1.5 parts of dispersing agent and 25 parts of solvent.
Wherein the modified polyurethane resin comprises the following raw materials in parts by weight: 13 parts of polyester polyol, 1.5 parts of dihydroxypolydimethylsiloxane, 10 parts of 3- (triethoxysilyl) propyl isocyanate, 2 parts of chain extender and 0.6 part of initiator.
Wherein the modified polyurethane resin is prepared by the following steps:
s1, adding polyester polyol, an initiator and dihydroxy polydimethylsiloxane into a reaction device according to parts by weight, uniformly mixing, heating to 35 ℃ and reacting to obtain silane grafted polyol for later use;
s2, adding the silane grafted polyol, 3- (triethoxysilyl) propyl isocyanate and a chain extender into a reaction device, uniformly mixing, heating to 45 ℃ and reacting to obtain the modified polyurethane resin.
Wherein, the modified nano titanium dioxide is prepared by the following method: 2 parts of silane coupling agent kh550 is dissolved in 50 parts of deionized water, 6 parts of nano titanium dioxide is added after uniform stirring, stirring is continued for 75 minutes, heating is carried out to 63 ℃, and moisture is dried, so that the modified nano titanium dioxide is obtained.
Wherein the defoamer is polyether modified organic silicon defoamer and F-1658 polyether modified silicon defoamer produced by Guangdong Tianfeng defoamer Co.
The cross-linking agent is polycarbodiimide cross-linking agent, which is supplied by Shanghai You En chemical company.
The dispersing agent is phosphate type high molecular polymer dispersing agent.
The solvent is ethyl acetate.
The protective layer coating for the cold stamping film is prepared by the following steps:
1) Adding the hydroxy acrylic resin, the modified polyurethane resin, the polyisocyanate and the modified nano titanium dioxide into a solvent according to parts by weight, uniformly stirring, and standing to obtain a mixed solution A for later use;
2) And mixing polytetrafluoroethylene, a defoaming agent, a cross-linking agent and a dispersing agent according to parts by weight, adding the mixture into the mixed solution A, heating to 45 ℃, and stirring for 1.5 hours to obtain the protective layer coating.
Example 3
The protective layer coating for the cold stamping film comprises the following raw materials in parts by weight: 3 parts of polytetrafluoroethylene, 30 parts of hydroxy acrylic resin, 15 parts of modified polyurethane resin, 3 parts of polyisocyanate, 2 parts of modified nano titanium dioxide, 2 parts of defoamer, 3 parts of cross-linking agent, 2 parts of dispersing agent and 30 parts of solvent.
Wherein the modified polyurethane resin comprises the following raw materials in parts by weight: 15 parts of polyester polyol, 2 parts of dihydroxypolydimethylsiloxane, 12 parts of 3- (triethoxysilyl) propyl isocyanate, 3 parts of chain extender and 0.8 part of initiator.
Wherein the modified polyurethane resin is prepared by the following steps:
s1, adding polyester polyol, an initiator and dihydroxy polydimethylsiloxane into a reaction device according to parts by weight, uniformly mixing, heating to 40 ℃ and reacting to obtain silane grafted polyol for later use;
s2, adding the silane grafted polyol, 3- (triethoxysilyl) propyl isocyanate and a chain extender into a reaction device, uniformly mixing, heating to 50 ℃ and reacting to obtain the modified polyurethane resin.
Wherein, the modified nano titanium dioxide is prepared by the following method: and 3 parts of silane coupling agent kh550 is dissolved in 60 parts of deionized water, 7 parts of nano titanium dioxide is added after uniform stirring, stirring is continued for 90min, heating is carried out to 65 ℃, and moisture is dried, so that the modified nano titanium dioxide is obtained.
Wherein the defoamer is polyether modified organic silicon defoamer and F-1658 polyether modified silicon defoamer produced by Guangdong Tianfeng defoamer Co.
The cross-linking agent is polycarbodiimide cross-linking agent, which is supplied by Shanghai You En chemical company.
The dispersant is an acrylate dispersant.
The solvent is butanone.
The protective layer coating for the cold stamping film is prepared by the following steps:
1) Adding the hydroxy acrylic resin, the modified polyurethane resin, the polyisocyanate and the modified nano titanium dioxide into a solvent according to parts by weight, uniformly stirring, and standing to obtain a mixed solution A for later use;
2) And mixing polytetrafluoroethylene, a defoaming agent, a cross-linking agent and a dispersing agent according to parts by weight, adding the mixture into the mixed solution A, heating to 50 ℃, and stirring for 2 hours to obtain the protective layer coating.
Example 4
The protective layer coating for the cold stamping film comprises the following raw materials in parts by weight: 4 parts of polytetrafluoroethylene, 35 parts of hydroxy acrylic resin, 18 parts of modified polyurethane resin, 4 parts of polyisocyanate, 2.5 parts of modified nano titanium dioxide, 2.5 parts of defoamer, 4 parts of cross-linking agent, 2.5 parts of dispersing agent and 35 parts of solvent.
Wherein the modified polyurethane resin comprises the following raw materials in parts by weight: 18 parts of polyester polyol, 2.5 parts of dihydroxypolydimethylsiloxane, 14 parts of 3- (triethoxysilyl) propyl isocyanate, 4 parts of chain extender and 0.9 part of initiator.
Wherein the modified polyurethane resin is prepared by the following steps:
s1, adding polyester polyol, an initiator and dihydroxy polydimethylsiloxane into a reaction device according to parts by weight, uniformly mixing, heating to 45 ℃ and reacting to obtain silane grafted polyol for later use;
s2, adding the silane grafted polyol, 3- (triethoxysilyl) propyl isocyanate and a chain extender into a reaction device, uniformly mixing, heating to 55 ℃ and reacting to obtain the modified polyurethane resin.
Wherein, the modified nano titanium dioxide is prepared by the following method: dissolving 4 parts of a silane coupling agent kh550 in 70 parts of deionized water, uniformly stirring, adding 8 parts of nano titanium dioxide, continuously stirring for 105min, heating to 68 ℃, and drying the water to obtain the modified nano titanium dioxide.
Wherein the defoamer is polyether modified organic silicon defoamer and F-1658 polyether modified silicon defoamer produced by Guangdong Tianfeng defoamer Co.
The cross-linking agent is polycarbodiimide cross-linking agent, which is supplied by Shanghai You En chemical company.
The dispersant is a polycarboxylic acid polymer dispersant.
The solvent is n-propyl ester.
The protective layer coating for the cold stamping film is prepared by the following steps:
1) Adding the hydroxy acrylic resin, the modified polyurethane resin, the polyisocyanate and the modified nano titanium dioxide into a solvent according to parts by weight, uniformly stirring, and standing to obtain a mixed solution A for later use;
2) And mixing polytetrafluoroethylene, a defoaming agent, a cross-linking agent and a dispersing agent according to parts by weight, adding the mixture into the mixed solution A, heating to 55 ℃, and stirring for 2.5 hours to obtain the protective layer coating.
Example 5
The protective layer coating for the cold stamping film comprises the following raw materials in parts by weight: 5 parts of polytetrafluoroethylene, 40 parts of hydroxy acrylic resin, 20 parts of modified polyurethane resin, 5 parts of polyisocyanate, 3 parts of modified nano titanium dioxide, 3 parts of defoamer, 5 parts of cross-linking agent, 3 parts of dispersing agent and 40 parts of solvent.
Wherein the modified polyurethane resin comprises the following raw materials in parts by weight: 20 parts of polyester polyol, 3 parts of dihydroxypolydimethylsiloxane, 16 parts of 3- (triethoxysilyl) propyl isocyanate, 5 parts of chain extender and 1.0 part of initiator.
Wherein the modified polyurethane resin is prepared by the following steps:
s1, adding polyester polyol, an initiator and dihydroxy polydimethylsiloxane into a reaction device according to parts by weight, uniformly mixing, heating to 50 ℃ for reaction to obtain silane grafted polyol for later use;
s2, adding the silane grafted polyol, 3- (triethoxysilyl) propyl isocyanate and a chain extender into a reaction device, uniformly mixing, heating to 60 ℃ and reacting to obtain the modified polyurethane resin.
Wherein, the modified nano titanium dioxide is prepared by the following method: and 5 parts of silane coupling agent kh550 is dissolved in 80 parts of deionized water, 9 parts of nano titanium dioxide is added after uniform stirring, stirring is continued for 120min, heating is carried out to 70 ℃, and moisture is dried, so that the modified nano titanium dioxide is obtained.
Wherein the defoamer is polyether modified organic silicon defoamer and F-1658 polyether modified silicon defoamer produced by Guangdong Tianfeng defoamer Co.
The cross-linking agent is polycarbodiimide cross-linking agent, which is supplied by Shanghai You En chemical company.
The dispersant is a polycarboxylic acid polymer dispersant.
The solvent is a mixture of cyclohexanone and butanone in a weight ratio of 8:7.
The protective layer coating for the cold stamping film is prepared by the following steps:
1) Adding the hydroxy acrylic resin, the modified polyurethane resin, the polyisocyanate and the modified nano titanium dioxide into a solvent according to parts by weight, uniformly stirring, and standing to obtain a mixed solution A for later use;
2) And mixing polytetrafluoroethylene, a defoaming agent, a cross-linking agent and a dispersing agent according to parts by weight, adding the mixture into the mixed solution A, heating to 60 ℃, and stirring for 3 hours to obtain the protective layer coating.
Comparative example 1
This comparative example differs from example 3 above in that: the polyurethane resin was not modified in the raw materials of the protective layer coating of the present comparative example. The remainder of this comparative example is the same as in example 3 and will not be described here again.
Comparative example 2
This comparative example differs from example 3 above in that: the raw materials of the protective layer coating of this comparative example were not added with polyisocyanate and polytetrafluoroethylene. The remainder of this comparative example is the same as in example 3 and will not be described here again.
The protective layer paints prepared in example 3 and comparative examples 1 to 2 were subjected to performance test, and the results are shown in table 1.
Sample preparation: the protective layer coatings prepared in the example 3 and the comparative examples 1-2 are respectively coated on aluminized electric aluminum gold stamping films, and the dry weight of the coated protective layers is set to be 1.5g/m 2 And (5) heating and curing to obtain the alumite gold stamping film sample coated with the protective layer.
Thermoprinting: and (3) coating cold-stamping UV glue on a printing stock (white cardboard for testing), attaching the sample to the surface of the UV glue, carrying out light irradiation curing, and stripping the base film of the gold stamping film to obtain the printing stock (namely the tested stock) with gold stamping patterns on the surface.
And (3) testing the attachment fastness of hot stamping: the 3M test adhesive tape is attached to the gold stamping patterns, after the 3M test adhesive tape is horizontally rolled back and forth for 3 times by a 2kg roller, the test adhesive tape is torn off, the gold stamping patterns still remained on a printing stock are observed, the adhesion fastness is expressed as a percentage of the area of the remained patterns (100% indicates that the adhesive tape does not stick any gold stamping patterns, the adhesion fastness is the best, 0% indicates that the adhesive tape sticks all gold stamping patterns, and the adhesion fastness is the worst).
Scratch resistance was tested: and testing the scratch resistance of the surface of the gold stamping pattern by adopting a friction testing machine. The invention uses a steel wool abrasion resistance tester with model number ZJ-339-GSR of Shenzhen Zhen Jiajia instruments and equipments limited company. The friction pressure of the sliding block is set to be 20N, the friction frequency is 40 times/min, the sliding block rubs back and forth on the surface of the gold stamping pattern, and the number of the sliding block reciprocating times when the surface starts to be scratched is recorded.
Test gloss: and testing the glossiness of the surface of the gold stamping pattern by adopting a glossiness meter. The invention uses a gloss meter with the model of WGG60 of Shanghai Mary instruments and meters Limited company, and the test method refers to the requirements of national standard GB/T9754-2007.
TABLE 1
| Project | Example 3 | Comparative example 1 | Comparative example 2 |
| Hot stamping attachment fastness/% | 90-95 | 60-70 | 65-75 |
| Scratch resistance/times | 70-75 | 40-43 | 50-55 |
| Gloss test (60 °)/° | 70 | 40 | 50 |
The test result of the embodiment 3 shows that the protective layer coating prepared by the invention has the advantages of better thermoprint adhesion fastness, scratch resistance and other mechanical properties, good glossiness and the like.
As can be seen from the comparison of the test results of the example 3 and the comparative examples 1-2, the addition of the modified polyurethane resin, the polyisocyanate and the polytetrafluoroethylene in the formulation under the same conditions can lead the prepared protective layer coating to have the advantages of better thermoprint adhesion fastness, scratch resistance and other mechanical properties, good glossiness and the like, and has wide market prospect and application value.
The above embodiments are preferred embodiments of the present invention, and besides, the present invention may be implemented in other ways, and any obvious substitution is within the scope of the present invention without departing from the concept of the present invention.
Claims (10)
1. A protective layer coating for a cold stamping film is characterized in that: the material comprises the following raw materials in parts by weight: 1-5 parts of polytetrafluoroethylene, 20-40 parts of hydroxy acrylic resin, 10-20 parts of modified polyurethane resin, 1-5 parts of polyisocyanate, 1-3 parts of modified nano titanium dioxide, 1-3 parts of defoamer, 1-5 parts of cross-linking agent, 1-3 parts of dispersing agent and 20-40 parts of solvent.
2. The protective layer coating for cold stamping films according to claim 1, wherein: the material comprises the following raw materials in parts by weight: 1-5 parts of polytetrafluoroethylene, 20-30 parts of hydroxy acrylic resin, 10-20 parts of modified polyurethane resin, 1-5 parts of polyisocyanate, 1-3 parts of modified nano titanium dioxide, 1-3 parts of defoamer, 1-5 parts of cross-linking agent, 1-3 parts of dispersing agent and 20-40 parts of solvent.
3. The protective layer coating for cold stamping films according to claim 1, wherein: the modified polyurethane resin comprises the following raw materials in parts by weight: 10-20 parts of polyester polyol, 1-3 parts of dihydroxypolydimethylsiloxane, 8-16 parts of 3- (triethoxysilyl) propyl isocyanate, 1-5 parts of chain extender and 0.5-1.0 part of initiator.
4. A protective layer coating for a cold stamping film as claimed in claim 3, characterized in that: the modified polyurethane resin is prepared by the following steps:
s1, adding polyester polyol, an initiator and dihydroxy polydimethylsiloxane into a reaction device according to parts by weight, uniformly mixing, heating to 30-50 ℃ for reaction to obtain silane grafted polyol for later use;
s2, adding the silane grafted polyol, 3- (triethoxysilyl) propyl isocyanate and a chain extender into a reaction device, uniformly mixing, heating to 40-60 ℃ and reacting to obtain the modified polyurethane resin.
5. The protective layer coating for cold stamping films according to claim 1, wherein: the modified nano titanium dioxide is nano titanium dioxide treated by a coupling agent and is prepared by the following method: 1-5 parts of silane coupling agent kh550 is dissolved in 40-80 parts of deionized water, 5-9 parts of nano titanium dioxide is added after uniform stirring, stirring is continued for 60-120min, heating is carried out to 60-70 ℃, and moisture is dried, so that the modified nano titanium dioxide is obtained.
6. The protective layer coating for cold stamping films according to claim 1, wherein: the defoamer is polyether modified organic silicon defoamer.
7. The protective layer coating for cold stamping films according to claim 1, wherein: the cross-linking agent is a polycarbodiimide cross-linking agent.
8. The protective layer coating for cold stamping films according to claim 1, wherein: the dispersing agent is one or more of polycarboxylic acid polymer dispersing agent, phosphate type high polymer dispersing agent and acrylic ester dispersing agent.
9. The protective layer coating for cold stamping films according to claim 1, wherein: the solvent is one or more of ethyl acetate, n-propyl ester, cyclohexanone and butanone.
10. A method for preparing the protective layer coating for cold stamping films as claimed in any one of claims 1 to 9, characterized in that: the preparation method comprises the following steps:
1) Adding the hydroxy acrylic resin, the modified polyurethane resin, the polyisocyanate and the modified nano titanium dioxide into a solvent according to parts by weight, uniformly stirring, and standing to obtain a mixed solution A for later use;
2) According to the weight portions, polytetrafluoroethylene, a defoaming agent, a cross-linking agent and a dispersing agent are mixed and then added into the mixed solution A, heated to 40-60 ℃ and stirred for 1-3h, and the protective layer coating is obtained.
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