Halogen-free environment-friendly gold foil

Abstract

The present application belongs to the technical field of gold foil, and particularly relates to a halogen-free environment-friendly gold foil. The halogen-free environment-friendly gold foil comprises a base film, a release layer, a colored coating layer, an aluminum plating layer and a back adhesive coating layer. The colored coating layer comprises the following components in parts by weight: 40-50 parts of modified acrylic resin, 6-8 parts of fatty acid ester, 3-5 parts of metal powder and 10-15 parts of auxiliary agent. The back adhesive coating layer comprises the following components in parts by weight: 30-40 parts of modified acrylic resin, 20-30 parts of water-based polyurethane resin, 8-10 parts of silicone oil, 0.4-0.6 parts of dispersing agent and 15-20 parts of ethylene glycol. The gold foil provided by the present application does not contain halogen, and neither the colored coating layer nor the back adhesive coating layer contains difficult-to-volatilize organic solvents. The water-based polymer resin is selected, and the environmental protection performance is better. The prepared gold foil has good mechanical properties, wear resistance and aging resistance, is used for gold blocking patterns, has good gold blocking effect, and the gold blocked patterns are flat and solid, have no burrs and no gold flying, and have no powder falling phenomenon after washing.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of gold foil, and particularly relates to a halogen-free environment-friendly gold foil. BACKGROUND

[0002] Gold foil, also known as electrochemical aluminum foil or stamping foil, is a special material used in the process of stamping on the surface of materials such as paper, plastic, leather, fabric, etc. It transfers the metal or pigment layer from the foil to the surface of the printing material through hot pressing transfer, forming patterns, characters or decorations with metallic luster or special effects to improve the grade and attractiveness of the product. Gold foil has the advantages of strong decoration, wear resistance, environmental protection, safety, flexible process, etc., and is widely used in packaging printing, bookbinding, card making, trademark identification, decorative materials and other fields. Gold foil is usually composed of multiple layers of materials, and its main structure includes a base layer, a separation layer, a coloring layer, an aluminum plating layer and an adhesive layer. The base layer is usually made of polyester film (such as PET) as a support layer to ensure the strength and stability of the foil during stamping. The separation layer is located on the base layer and separates the foil from the base layer during stamping to ensure that the metal or pigment layer can be smoothly transferred to the printing material. The coloring layer is composed of pigments or dyes, which can give the gold foil a specific color. The aluminum plating layer is a very thin metal aluminum film formed on the coloring layer by vacuum aluminum plating process to produce a metallic luster effect. The adhesive layer is the outermost layer composed of adhesive, which can firmly adhere the metal or pigment layer on the foil to the surface of the printing material.

[0003] A color layer paint and an electrochemical aluminum stamping foil with the same are disclosed in Chinese patent application No. CN202311515305.1. The color layer paint includes the following raw materials by weight: acrylic resin 30-45 parts; acrylic acid 20-30 parts; polyacrylamide 5-8 parts; organosiloxane 5-7 parts; a mixture of acetone and butyl glycidyl ether 10-20 parts; polyvinyl chloride 6-10 parts; acrylic acid polyethylene glycol diester 10-15 parts; vinyl ether 5-9 parts; initiator 0.02-0.1 parts; sodium hexametaphosphate 3-5 parts; dye 10-30 parts; inorganic sheet material 10-18 parts; auxiliary agent 3-7 parts; deionized water in appropriate amount. The color layer paint and the electrochemical aluminum stamping foil with the same can significantly improve the stamping defects such as "gold flying" and "powder falling" during the use of the electrochemical aluminum stamping foil, and improve the stamping quality and production efficiency. However, the color layer formed by the color layer paint has insufficient aging resistance, and the color and gloss of the color layer are affected after long-term exposure to air. With the continuous enhancement of people's environmental awareness, water-based adhesives are mostly used to replace solvent-based adhesives for the adhesive layer of gold foil to obtain a safe and environmentally friendly adhesive layer, meeting the environmental protection requirements of gold foil. SUMMARY

[0004] The present application aims at solving the problems of the prior art, and provides a halogen-free environment-friendly gold foil, which is free of halogen and does not contain volatile organic solvents in the coloring coating and the back adhesive coating, and is made of water-based polymer resin, so that the environment-friendly performance is better, and the gold foil has good mechanical properties, wear resistance and aging resistance, and is used for gold blocking patterns, so that the gold blocking effect is good, the gold blocking pattern is flat and solid, has no burrs and gold flying, and has no powder falling after washing.

[0005] The present application adopts the following technical scheme to achieve the above-mentioned purpose:

[0006] The halogen-free environment-friendly gold foil comprises a base film, a release layer, a coloring coating, an aluminum plating layer and a back adhesive coating.

[0007] Further, the coloring coating comprises the following components in parts by weight: 40-50 parts of modified acrylic resin, 6-8 parts of fatty acid ester, 3-5 parts of metal powder and 10-15 parts of auxiliary agent.

[0008] Further, the fatty acid ester in the coloring coating is glycerol monostearate or glycerol monooleate; the metal powder is silver powder, gold powder or copper-gold powder; and the auxiliary agent is ethylene glycol or propylene glycol.

[0009] Further, the back adhesive coating comprises the following components in parts by weight: 30-40 parts of modified acrylic resin, 20-30 parts of water-based polyurethane resin, 8-10 parts of silicone oil, 0.4-0.6 parts of dispersant and 15-20 parts of ethylene glycol.

[0010] Further, the silicone oil in the back adhesive coating is methyl silicone oil or dimethyl silicone oil; and the dispersant is EFKA-4560 or EFKA-1503.

[0011] In the technical scheme of the present application, the modified acrylic resin in the coloring coating and the back adhesive coating is obtained by polymerization of methyl methacrylate, butyl acrylate, acrylic acid and alkenylized nanodiamond.

[0012] Further, the preparation method of the modified acrylic resin is as follows: methyl methacrylate, butyl acrylate, acrylic acid and alkenylized nanodiamond are added to deionized water, stirred and mixed uniformly, 50-60wt% ammonium persulfate aqueous solution is slowly added dropwise under nitrogen protection at a temperature of 75-80℃, the temperature is increased to 85-90℃ after the dropwise addition is completed, and the reaction is kept for 1.5-2h, so that the modified acrylic resin is obtained.

[0013] Further, the mass ratio of the methyl methacrylate, butyl acrylate, acrylic acid, alkenylized nanodiamond and deionized water is 1:1.5-2:0.2-0.3:0.5-0.6:4-5.

[0014] Further, the amount of ammonium persulfate is 0.2-0.3% of the total mass of methyl methacrylate, butyl acrylate, acrylic acid and alkenyl nanodiamond.

[0015] In the technical scheme of the present application, the preparation method of the alkenyl nanodiamond is as follows:

[0016] S1, nanodiamond is added to an alcohol aqueous solution of silane, and stirred at a temperature of 50-60℃ for 4-5h, after the reaction is completed, the product is filtered, washed with ethanol, and dried to obtain chlorinated nanodiamond;

[0017] S2, the chlorinated nanodiamond is added to ethanol, stirred uniformly, 2-vinyl benzimidazole and triethylamine are added, and stirred at 60-70℃ for 5-6h, after the reaction is completed, the product is filtered, washed with ethanol, and dried to obtain alkenyl nanodiamond.

[0018] Further, the mass ratio of nanodiamond to the alcohol aqueous solution of silane in step S1 is 1:10-15.

[0019] Further, the preparation method of the alcohol aqueous solution of silane in step S1 is as follows: 3-chloropropyltrimethoxysilane, water and methanol are mixed uniformly according to a mass ratio of 0.1-0.2:4:6, and the pH value is adjusted to 5-6 to obtain the alcohol aqueous solution of silane.

[0020] Further, the mass ratio of chlorinated nanodiamond, 2-vinyl benzimidazole and triethylamine in step S2 is 1:0.1-0.2:0.05-0.1.

[0021] The present application has the following beneficial effects:

[0022] The modified acrylic resin is polymerized by methyl methacrylate, butyl acrylate, acrylic acid and alkenylized nanodiamond, wherein the alkenylized nanodiamond is prepared by the following steps: nanodiamond is used as raw material, and is reacted with an alcohol aqueous solution of silane to introduce chloroalkyl on the surface of the nanodiamond, and then the chloroalkyl is reacted with 2-vinyl benzimidazole to further introduce vinyl and benzimidazole groups on the surface of the nanodiamond, thereby obtaining the alkenylized nanodiamond; the compatibility of the modified nanodiamond, i.e., the alkenylized nanodiamond, with the organic component is better, and the modified nanodiamond can participate in the polymerization of monomers to form a modified acrylic resin containing nanodiamond and benzimidazole groups in the structure, thereby being closely attached to the surface of a substrate to enhance the compactness of a coating; since the nanodiamond has good oxidation resistance and hardness, and the benzimidazole group also has certain oxidation resistance and rigidity, the presence of the nanodiamond and the benzimidazole group can cooperate with each other to improve the mechanical properties, wear resistance and aging resistance of the gold foil; the coloring coating and the back adhesive coating of the gold foil both contain the modified acrylic resin, and the coloring coating and the back adhesive coating synergistically work to greatly enhance the mechanical properties, wear resistance and aging resistance of the gold foil.

[0023] The gold foil provided by the present application does not contain halogen, and neither the coloring coating nor the back adhesive coating contains difficult-to-volatilize organic solvents, and a water-based polymer resin is selected, so that the environmental protection performance is better, and the prepared gold foil has good mechanical properties, wear resistance and aging resistance, and is used for hot stamping patterns, and has good hot stamping effect, and the hot stamping patterns are flat and solid, have no burrs and no gold flying, and have no powder falling phenomenon after washing. DETAILED DESCRIPTION

[0024] To make the objectives, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described below in a clear and complete manner in combination with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments of the present application; as long as the technical features designed in the different embodiments of the present application do not conflict with each other, they can be combined with each other; based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0025] In the technical scheme of the present application, all the chemical reagents used are ordinary commercially available, wherein the glycerol monostearate has a CAS number of 31566-31-1, the glycerol monooleate has a CAS number of 25496-72-4, the aqueous polyurethane resin is MR-878, the methyl silicone oil has a CAS number of 8050-81-5, the dimethyl silicone oil has a CAS number of 9006-65-9, the methyl methacrylate has a CAS number of 80-62-6, the butyl acrylate has a CAS number of 141-32-2, the acrylic acid has a CAS number of 79-10-7, the ammonium persulfate has a CAS number of 7727-54-0, the nano diamond has a CAS number of 7782-40-3, the 3-chloropropyl trimethoxysilane has a CAS number of 2530-87-2, the 2-vinylbenzimidazole has a CAS number of 14984-26-0, the triethylamine has a CAS number of 121-44-8, the ethylene glycol has a CAS number of 107-21-1, the propylene glycol has a CAS number of 57-55-6, the methanol has a CAS number of 67-56-1, and the ethanol has a CAS number of 64-17-5.

[0026] Example I

[0027] A halogen-free environment-friendly gold foil, which comprises a base film, a release layer, a colored coating layer, an aluminum plating layer and a back adhesive coating layer.

[0028] The colored coating layer comprises the following components in parts by weight: 50 parts of modified acrylic resin, 8 parts of fatty acid ester, 5 parts of metal powder and 13 parts of auxiliary agent; wherein the fatty acid ester is glycerol monostearate, the metal powder is silver powder, and the auxiliary agent is ethylene glycol.

[0029] The back adhesive coating layer comprises the following components in parts by weight: 40 parts of modified acrylic resin, 25 parts of aqueous polyurethane resin, 10 parts of silicone oil, 0.6 parts of dispersant and 20 parts of ethylene glycol; wherein the silicone oil is methyl silicone oil, and the dispersant is EFKA-4560.

[0030] The modified acrylic resin in the colored coating layer and the back adhesive coating layer is obtained by polymerization of methyl methacrylate, butyl acrylate, acrylic acid and alkenylized nano diamond, and the preparation method of the modified acrylic resin is as follows:

[0031] Methyl methacrylate, butyl acrylate, acrylic acid and alkenylized nano diamond are added to deionized water, stirred and uniformly mixed, 60wt% ammonium persulfate aqueous solution is slowly added dropwise under nitrogen protection at a temperature of 80℃, after the dropwise addition is completed, the temperature is raised to 90℃, and the reaction is kept for 1.5h, and the modified acrylic resin is obtained after the reaction is completed; wherein the mass ratio of methyl methacrylate, butyl acrylate, acrylic acid, alkenylized nano diamond and deionized water is 1:2:0.3:0.6:5; the amount of ammonium persulfate is 0.3% of the total mass of methyl methacrylate, butyl acrylate, acrylic acid and alkenylized nano diamond.

[0032] The preparation method of the alkenylated nanodiamond is as follows:

[0033] S1, nanodiamond is added to the alcohol aqueous solution of silane, stirring at a temperature of 60℃ for 5h, after the reaction is completed, filtering, the product is washed with ethanol, and after drying, chlorinated nanodiamond is obtained; wherein the mass ratio of nanodiamond and the alcohol aqueous solution of silane is 1:15; the preparation method of the alcohol aqueous solution of silane is as follows: 3-chloropropyl trimethoxysilane, water and methanol are mixed uniformly according to a mass ratio of 0.2:4:6, and the pH value is adjusted to 6 to obtain the alcohol aqueous solution of silane;

[0034] S2, chlorinated nanodiamond is added to ethanol, stirring uniformly, then 2-vinyl benzimidazole and triethylamine are added, and stirring is carried out at 70℃ for 5h, after the reaction is completed, filtering, the product is washed with ethanol, and after drying, alkenylated nanodiamond is obtained; wherein the mass ratio of chlorinated nanodiamond, 2-vinyl benzimidazole and triethylamine is 1:0.2:0.1.

[0035] Example two

[0036] A halogen-free and environmentally friendly gilding foil, the gilding foil comprising a base film, a release layer, a colored coating layer, an aluminum plating layer and a back adhesive coating layer.

[0037] The colored coating layer comprises the following components by weight: 45 parts of modified acrylic resin, 7 parts of fatty acid ester, 4 parts of metal powder and 15 parts of auxiliary agent; wherein the fatty acid ester is glycerol monooleate; the metal powder is gold powder; and the auxiliary agent is propylene glycol.

[0038] The back adhesive coating layer comprises the following components by weight: 35 parts of modified acrylic resin, 30 parts of water-based polyurethane resin, 9 parts of silicone oil, 0.5 parts of dispersant and 15 parts of ethylene glycol; wherein the silicone oil is dimethyl silicone oil; and the dispersant is EFKA-1503.

[0039] The modified acrylic resin in the colored coating layer and the back adhesive coating layer is obtained by polymerization of methyl methacrylate, butyl acrylate, acrylic acid and alkenylated nanodiamond, and the preparation method of the modified acrylic resin is as follows:

[0040] Methyl methacrylate, butyl acrylate, acrylic acid and alkenylated nanodiamond are added to deionized water, stirring and mixing uniformly, slowly dropping 50wt% ammonium persulfate aqueous solution under nitrogen protection, after the dropping is completed, the temperature is increased to 85℃, and the reaction is carried out for 2h, after the reaction is completed, the modified acrylic resin is obtained; wherein the mass ratio of methyl methacrylate, butyl acrylate, acrylic acid, alkenylated nanodiamond and deionized water is 1:1.5:0.2:0.5:4; and the amount of ammonium persulfate is 0.2% of the total mass of methyl methacrylate, butyl acrylate, acrylic acid and alkenylated nanodiamond.

[0041] The preparation method of the alkenylated nanodiamond is as follows:

[0042] S1, nanodiamond is added to an alcohol aqueous solution of silane, stirring at a temperature of 55℃ for 4h, after the reaction is completed, filtering, the product is washed with ethanol, and after drying, chlorinated nanodiamond is obtained; wherein the mass ratio of nanodiamond, alcohol aqueous solution of silane is 1:12; the preparation method of the alcohol aqueous solution of silane is as follows: 3-chloropropyl trimethoxysilane, water and methanol are mixed uniformly according to a mass ratio of 0.1:4:6, and the pH value is adjusted to 5 to obtain the alcohol aqueous solution of silane;

[0043] S2, chlorinated nanodiamond is added to ethanol, stirring uniformly, then 2-vinyl benzimidazole and triethylamine are added, stirring at 65℃ for 6h, after the reaction is completed, filtering, the product is washed with ethanol, and after drying, alkenylated nanodiamond is obtained; wherein the mass ratio of chlorinated nanodiamond, 2-vinyl benzimidazole, triethylamine is 1:0.15:0.06.

[0044] Example three

[0045] A halogen-free and environmentally friendly gilding foil, the gilding foil comprising a base film, a release layer, a colored coating layer, an aluminum plating layer and a back adhesive coating layer.

[0046] The colored coating layer comprises the following components by weight: 40 parts of modified acrylic resin, 6 parts of fatty acid ester, 3 parts of metal powder, 10 parts of auxiliary agent; wherein the fatty acid ester is glycerol monostearate; the metal powder is copper gold powder; the auxiliary agent is ethylene glycol.

[0047] The back adhesive coating layer comprises the following components by weight: 30 parts of modified acrylic resin, 20 parts of water-based polyurethane resin, 8 parts of silicone oil, 0.4 parts of dispersant, 18 parts of ethylene glycol; wherein the silicone oil is methyl silicone oil; the dispersant is EFKA-4560.

[0048] The modified acrylic resin in the colored coating layer and the back adhesive coating layer is obtained by polymerization of methyl methacrylate, butyl acrylate, acrylic acid and alkenylated nanodiamond, and the preparation method of the modified acrylic resin is as follows:

[0049] Methyl methacrylate, butyl acrylate, acrylic acid and alkenylated nanodiamond are added to deionized water, stirring and mixing uniformly, under nitrogen protection, a 55wt% ammonium persulfate aqueous solution is slowly added dropwise at a temperature of 78℃, after the dropwise addition is completed, the temperature is raised to 88℃, and the reaction is kept for 1.8h, after the reaction is completed, the modified acrylic resin is obtained; wherein the mass ratio of methyl methacrylate, butyl acrylate, acrylic acid, alkenylated nanodiamond and deionized water is 1:1.6:0.25:0.55:4.5; the amount of ammonium persulfate is 0.25% of the total mass of methyl methacrylate, butyl acrylate, acrylic acid and alkenylated nanodiamond.

[0050] The preparation method of the alkenylated nanodiamond is as follows:

[0051] S1, the nanodiamond is added into the alcohol aqueous solution of silane, and stirred at a temperature of 50℃ for 4.5h, after the reaction is completed, the product is washed with ethanol, and dried to obtain the chlorinated nanodiamond; wherein the mass ratio of the nanodiamond and the alcohol aqueous solution of silane is 1:10; the alcohol aqueous solution of silane is prepared by mixing 3-chloropropyltrimethoxysilane, water and methanol in a mass ratio of 0.15:4:6, and adjusting the pH value to 5.5;

[0052] S2, the chlorinated nanodiamond is added into ethanol, stirred uniformly, and then 2-vinyl benzimidazole and triethylamine are added, and stirred at 60℃ for 5.5h, after the reaction is completed, the product is filtered, washed with ethanol, and dried to obtain the alkenylated nanodiamond; wherein the mass ratio of the chlorinated nanodiamond, 2-vinyl benzimidazole and triethylamine is 1:0.1:0.05.

[0053] Example Four

[0054] A halogen-free and environmentally friendly gold foil, the gold foil comprising a base film, a release layer, a colored coating layer, an aluminum plating layer and a back adhesive coating layer.

[0055] The colored coating layer comprises the following components by weight: 50 parts of modified acrylic resin, 6 parts of fatty acid ester, 4 parts of metal powder, 14 parts of auxiliary agent; wherein the fatty acid ester is glycerol monostearate; the metal powder is gold powder; and the auxiliary agent is propylene glycol.

[0056] The back adhesive coating layer comprises the following components by weight: 40 parts of modified acrylic resin, 30 parts of water-based polyurethane resin, 8 parts of silicone oil, 0.5 parts of dispersant, and 16 parts of ethylene glycol; wherein the silicone oil is methyl silicone oil; and the dispersant is EFKA-1503.

[0057] The modified acrylic resin in the colored coating layer and the back adhesive coating layer is obtained by polymerization of methyl methacrylate, butyl acrylate, acrylic acid and alkenylated nanodiamond, and the preparation method of the modified acrylic resin is as follows:

[0058] Methyl methacrylate, butyl acrylate, acrylic acid, alkenylized nanodiamond are added into deionized water, stirred and mixed uniformly, 55wt% ammonium persulfate aqueous solution is slowly added dropwise under nitrogen protection at 80℃, after dropwise addition, the temperature is increased to 85℃, and the reaction is kept for 1.6h, after the reaction is completed, the modified acrylic resin is obtained; wherein the mass ratio of methyl methacrylate, butyl acrylate, acrylic acid, alkenylized nanodiamond and deionized water is 1:1.5:0.3:0.5:5; the amount of ammonium persulfate is 0.2% of the total mass of methyl methacrylate, butyl acrylate, acrylic acid and alkenylized nanodiamond.

[0059] The preparation method of the alkenylized nanodiamond is as follows:

[0060] S1, nanodiamond is added into the alcohol aqueous solution of silane, stirred and reacted at 55℃ for 5h, after the reaction is completed, the product is filtered, washed with ethanol, and dried to obtain chlorinated nanodiamond; wherein the mass ratio of nanodiamond and alcohol aqueous solution of silane is 1:14; the alcohol aqueous solution of silane is prepared by mixing 3-chloropropyltrimethoxysilane, water and methanol in a mass ratio of 0.2:4:6, and adjusting the pH value to 5;

[0061] S2, chlorinated nanodiamond is added into ethanol, stirred and mixed uniformly, then 2-vinyl benzimidazole and triethylamine are added, and stirred and reacted at 60℃ for 6h, after the reaction is completed, the product is filtered, washed with ethanol, and dried to obtain alkenylized nanodiamond; wherein the mass ratio of chlorinated nanodiamond, 2-vinyl benzimidazole and triethylamine is 1:0.1:0.1.

[0062] Comparative Example One

[0063] In this comparative example, the colored coating component does not contain modified acrylic resin compared with Example One.

[0064] A halogen-free and environmentally friendly gold foil, the gold foil comprises a base film, a release layer, a colored coating layer, an aluminum plating layer and a back adhesive coating layer.

[0065] The colored coating layer comprises the following components by weight: 50 parts of acrylic resin, 8 parts of fatty acid ester, 5 parts of metal powder, 13 parts of auxiliary agent; wherein the fatty acid ester is glycerol monostearate; the metal powder is silver powder; and the auxiliary agent is ethylene glycol.

[0066] The back adhesive coating layer comprises the following components by weight: 40 parts of modified acrylic resin, 25 parts of water-based polyurethane resin, 10 parts of silicone oil, 0.6 parts of dispersant, and 20 parts of ethylene glycol; wherein the silicone oil is methyl silicone oil; and the dispersant is EFKA-4560.

[0067] The acrylic resin in the colored coating is obtained by polymerization of methyl methacrylate, butyl acrylate and acrylic acid, and the preparation method of the acrylic resin is as follows:

[0068] Methyl methacrylate, butyl acrylate and acrylic acid are added into deionized water, stirred and uniformly mixed, and then 60wt% ammonium persulfate aqueous solution is slowly added dropwise under nitrogen protection at 80℃. After the dropwise addition is completed, the temperature is increased to 90℃, and the reaction is kept for 1.5h. After the reaction is completed, the acrylic resin is obtained. The mass ratio of methyl methacrylate, butyl acrylate, acrylic acid and deionized water is 1:2:0.3:5, and the amount of ammonium persulfate is 0.3% of the total mass of methyl methacrylate, butyl acrylate and acrylic acid.

[0069] The modified acrylic resin in the back adhesive coating is obtained by polymerization of methyl methacrylate, butyl acrylate, acrylic acid and alkenylized nanodiamond, and the preparation method of the modified acrylic resin is the same as that in Example 1.

[0070] The preparation method of the alkenylized nanodiamond is the same as that in Example 1.

[0071] Comparative Example 2

[0072] Compared with Example 1, the back adhesive coating component of the present comparative example does not contain modified acrylic resin.

[0073] A halogen-free and environmentally friendly gold foil, the gold foil comprising a base film, a release layer, a colored coating, an aluminum plating layer and a back adhesive coating.

[0074] The colored coating comprises the following components by weight: 50 parts of modified acrylic resin, 8 parts of fatty acid ester, 5 parts of metal powder and 13 parts of auxiliary agent; wherein the fatty acid ester is glycerol monostearate, the metal powder is silver powder, and the auxiliary agent is ethylene glycol.

[0075] The back adhesive coating comprises the following components by weight: 40 parts of acrylic resin, 25 parts of water-based polyurethane resin, 10 parts of silicone oil, 0.6 parts of dispersant and 20 parts of ethylene glycol; wherein the silicone oil is methyl silicone oil, and the dispersant is EFKA-4560.

[0076] The modified acrylic resin in the colored coating is obtained by polymerization of methyl methacrylate, butyl acrylate, acrylic acid and alkenylized nanodiamond, and the preparation method of the modified acrylic resin is the same as that in Example 1.

[0077] The acrylic resin in the back adhesive coating is obtained by polymerization of methyl methacrylate, butyl acrylate and acrylic acid, and the preparation method of the acrylic resin is the same as that in Comparative Example 1.

[0078] The preparation method of the alkenylized nanodiamond is the same as that in Example 1.

[0079] Comparative Example 3

[0080] Comparative Example 1, the coloring coating and the back adhesive coating do not contain modified acrylic resin.

[0081] A halogen-free and environmentally friendly gold foil, the gold foil comprising a base film, a release layer, a coloring coating, an aluminum plating layer, and a back adhesive coating.

[0082] The coloring coating comprises the following components by weight: 50 parts of acrylic resin, 8 parts of fatty acid ester, 5 parts of metal powder, and 13 parts of auxiliary agent; wherein the fatty acid ester is glycerol monostearate; the metal powder is silver powder; and the auxiliary agent is ethylene glycol.

[0083] The back adhesive coating comprises the following components by weight: 40 parts of acrylic resin, 25 parts of water-based polyurethane resin, 10 parts of silicone oil, 0.6 parts of dispersant, and 20 parts of ethylene glycol; wherein the silicone oil is methyl silicone oil; and the dispersant is EFKA-4560.

[0084] The acrylic resin in the coloring coating and the back adhesive coating is obtained by polymerization of methyl methacrylate, butyl acrylate, and acrylic acid, and the preparation method of the acrylic resin is the same as that of Comparative Example 1.

[0085] The halogen-free and environmentally friendly gold foils provided in Examples 1 to 4 and Comparative Examples 1 to 3 are tested for performance, and the preparation method of the gold foil is as follows: an organic silicone resin release layer coating is applied on a base film (PET film), dried to form a release layer, then a coloring coating coating (wet coating amount of 4 g / m 2 ) is applied on the release layer, dried to form a coloring coating, vacuum aluminum plating is performed on the coloring coating to form an aluminum plating layer, and finally a back adhesive coating coating is applied on the aluminum plating layer, dried, and a halogen-free and environmentally friendly gold foil is obtained; the tensile property test is performed in accordance with the GB / T 228.1-2021 standard; the wear resistance test is performed in accordance with the GB / T 6739-2006 standard; the aging resistance test conditions are as follows: a UVA-340 type ultraviolet aging lamp is used, the irradiance is 0.89 W·m -2 , 10 h of irradiation (temperature of 45℃), 2 h of condensation (temperature of 40℃), i.e. 12 h of one cycle, and the cycle is repeated for 6 times, and whether the gold foil appears discoloration and other aging phenomena is observed; the gold foil prepared is used for hot stamping on polyester fabric, the hot stamping effect is observed, and after the hot stamping is completed, the polyester fabric is washed for 20 times, and whether the hot stamping pattern appears powder dropping phenomenon is observed; and the test results are shown in Table 1.

[0086] Table 1 Performance test results

[0087]

[0088] As shown in Table 1, the gold foil prepared by the examples one to four has good mechanical properties, wear resistance and aging resistance, and the gold foil is used for hot stamping pattern, and the hot stamping effect is good, the hot stamping pattern is flat and solid, has no burr, no gold flying, and has good water resistance; compared with the comparative examples one to three, the coloring coating and the back adhesive coating containing the modified acrylic resin in the example one can effectively improve the mechanical properties, wear resistance, aging resistance and water resistance of the gold foil.

[0089] It should be noted that in this document, such as the term "comprise", "include" or any other variant thereof is intended to cover non-exclusive inclusion, so that the process, method, article or equipment including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or includes elements inherent to such process, method, article or equipment.

[0090] Although the embodiments of the present application have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made thereto without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A halogen-free, environmentally friendly hot stamping foil, characterized in that, The hot stamping foil includes a base film, a release layer, a coloring coating, an aluminum plating layer, and an adhesive coating. The coloring coating comprises the following components by weight: 40-50 parts modified acrylic resin, 6-8 parts fatty acid ester, 3-5 parts metal powder, and 10-15 parts additives. The adhesive coating comprises the following components by weight: 30-40 parts modified acrylic resin, 20-30 parts waterborne polyurethane resin, 8-10 parts silicone oil, 0.4-0.6 parts dispersant, and 15-20 parts ethylene glycol; The modified acrylic resin used in the coloring coating and adhesive coating is prepared as follows: methyl methacrylate, butyl acrylate, acrylic acid, and alkenylated nanodiamonds are added to deionized water, stirred and mixed evenly, and under nitrogen protection, a 50-60 wt% aqueous solution of ammonium persulfate is slowly added dropwise at a temperature of 75-80℃. After the addition is complete, the temperature is raised to 85-90℃ and the reaction is maintained for 1.5-2 hours. After the reaction is complete, the modified acrylic resin is obtained. The mass ratio of methyl methacrylate, butyl acrylate, acrylic acid, alkenylated nanodiamonds, and deionized water is 1:1.5-2:0.2-0.3:0.5-0.6:4-5. The preparation method of the alkenylated nanodiamond is as follows: S1. Add nanodiamond to an alcoholic aqueous solution of silane, stir and react at 50-60℃ for 4-5 hours. After the reaction is complete, filter, wash the product with ethanol, and dry to obtain chlorinated nanodiamond; the mass ratio of nanodiamond to the alcoholic aqueous solution of silane is 1:10-15. S2. Chlorinated nanodiamonds are added to ethanol and stirred until homogeneous. Then, 2-vinylbenzimidazole and triethylamine are added, and the mixture is stirred at 60-70°C for 5-6 hours. After the reaction is complete, the mixture is filtered, the product is washed with ethanol, and dried to obtain alkenylated nanodiamonds. The mass ratio of chlorinated nanodiamonds, 2-vinylbenzimidazole, and triethylamine is 1:0.1-0.2:0.05-0.

1.

2. The halogen-free environmentally friendly hot stamping foil according to claim 1, characterized in that, The amount of ammonium persulfate used is 0.2-0.3% of the total mass of methyl methacrylate, butyl acrylate, acrylic acid, and alkenylated nanodiamond.

3. The halogen-free environmentally friendly hot stamping foil according to claim 1, characterized in that, The method for preparing the silane alcohol-water solution in step S1 is as follows: 3-chloropropyltrimethoxysilane, water and methanol are mixed evenly according to a mass ratio of 0.1-0.2:4:6, and the pH value is adjusted to 5-6 to obtain the silane alcohol-water solution.

4. The halogen-free environmentally friendly hot stamping foil according to claim 1, characterized in that, The fatty acid ester in the coloring coating is glycerol monostearate or glycerol monooleate; the metal powder is silver powder, gold powder or copper-gold powder; and the additive is ethylene glycol or propylene glycol.

5. The halogen-free environmentally friendly hot stamping foil according to claim 1, characterized in that, The silicone oil in the adhesive coating is methyl silicone oil or dimethyl silicone oil; the dispersant is EFKA-4560 or EFKA-1503.

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