Scratch-resistant and wear-resistant silk-screen cold-stamping gold foil and preparation process thereof

Abstract

The invention discloses a scratch-resistant and wear-resistant silk-screen cold-stamping gold foil and a preparation process thereof, and belongs to the technical field of cold-stamping films. The scratch-resistant and wear-resistant silk-screen cold-stamping gold foil comprises a base film layer, a release coating coated on the base film layer, an imaging coating coated on the release coating, an aluminum layer plated on the imaging coating, and a protective coating coated on the aluminum layer, the imaging coating is prepared from the following raw material components in parts by weight: first composite acrylic resin, 800-1200-mesh bronze powder or toner, butanone and ethyl acetate; the protective coating is prepared from the following raw material components in parts by weight: second composite acrylic resin and xylene; the first composite acrylic resin is obtained by compounding a first acrylic resin copolymer and an antioxidant diphenylethylenediamine; the first acrylic resin copolymer is obtained by carrying out copolymerization on methyl methacrylate, hydroxyethyl methylacrylate, butyl acrylate and 3-allyl-2-hydroxybenzaldehyde.

Description

Technical Field

[0001] The invention relates to a scratch-resistant and wear-resistant silk-screen cold stamping gold foil and a preparation process thereof. Background Art

[0002] In recent years, cold stamping technology has been widely used and developed in the printing industry. Cold stamping technology is a process that uses a set of printing units as adhesive coating units to transfer the hot stamping foil to the substrate. Compared with traditional hot stamping technology, cold stamping has significant advantages. First of all, the cold stamping process needs to be completed in two steps: the first step is to accurately transfer the special glue to the surface of the substrate and ensure its firm adhesion; the second step is to transfer the hot stamping paper to the surface of the substrate by applying a certain amount of pressure, so as to transfer the graphic information to the sticky coated photosensitive layer.

[0003] The emergence of cold stamping technology has greatly enriched the performance of products and added more design options. It can beautify fonts and can more perfectly handle multi-level hot stamping effects, providing designers with more creative space. It is particularly worth mentioning that cold stamping technology can use ordinary flexible plates without the need to make expensive metal plates, which greatly reduces the cost of plate making and shortens the plate making cycle. At the same time, online hot stamping is fast and does not require heating, making the hot stamping process more applicable, even to temperature-sensitive substrates such as films and heat-sensitive materials.

[0004] Although cold stamping technology has shown strong competitiveness in the market, it still faces some technical challenges in practical applications. One of the most prominent problems is the quality of the cold transfer hot stamping coating. The existing cold transfer hot stamping coating often has poor leveling properties due to the high viscosity adhesive used, resulting in uneven coating, which affects the gloss and flatness of the hot stamping foil surface. This uneven surface will cause diffuse reflection, thereby affecting the color and gloss of the hot stamping image and text, and ultimately reducing the aesthetics of the product. Therefore, the development of a cold stamping hot stamping foil with good leveling, high gloss, scratch resistance and wear resistance and its preparation process has become a technical problem that needs to be solved urgently. Summary of the invention

[0005] The purpose of the present invention is to provide a scratch-resistant and wear-resistant silk-screen cold stamping gold foil and a preparation process thereof, so as to solve the technical problems mentioned in the above background technology.

[0006] The technical solution for achieving the purpose of the present invention is: A scratch-resistant and wear-resistant silk-screen cold stamping gold foil, comprising a base film layer, a release coating coated on the base film layer, an imaging coating coated on the release coating, an aluminum layer plated on the imaging coating, and a protective coating coated on the aluminum layer; The raw material components of the imaging coating include, by weight: 40-60 parts by weight of a first composite acrylic resin, 0-4 parts by weight of a coloring material, 30-50 parts by weight of butanone, and 3-10 parts by weight of ethyl acetate; the coloring material includes toner and copper-gold powder.

[0007] The base film is a PET film.

[0008] Furthermore, the raw material components of the release coating include, by weight: 5-10 parts by weight of aqueous oxidized polyethylene wax emulsion; 50-60 parts by weight of ethanol; and 30-40 parts by weight of water.

[0009] Furthermore, the raw material components of the protective coating include, by weight: 60-80 parts by weight of the second composite acrylic resin and 20-40 parts by weight of xylene.

[0010] Furthermore, the first composite acrylic resin is obtained by compounding a first acrylic resin copolymer and an antioxidant diphenylethylenediamine; the first acrylic resin copolymer is obtained by copolymerizing methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate and 3-allyl-2-hydroxybenzaldehyde.

[0011] Furthermore, the second composite acrylic resin is obtained by compounding a second acrylic resin copolymer and hydroxy silicone oil; The second acrylic resin copolymer is composed of methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate and silane coupling agent KH570.

[0012] The present invention also provides a preparation process of a scratch-resistant and wear-resistant silk-screen cold stamping gold foil, comprising the following preparation steps: S1. Prepare release coating: add ethanol and water into a stirring barrel according to the formula ratio, stir evenly at a constant temperature of 25~30°C for 5~15min, then add the aqueous oxidized polyethylene wax emulsion into the stirring barrel according to the proportion, stir while adding, and continue stirring for 30~60min after adding to obtain the release coating; S2. Prepare an imaging coating: add butanone to a stirring barrel according to the formula ratio, stir evenly at a constant temperature of 25 to 30 ° C for 5 to 15 minutes, and then add ethyl acetate, a first composite acrylic resin, and a coloring material to a stirring barrel in proportion, stirring while adding, and continue stirring for 23 to 25 hours after adding to obtain an imaging coating; S3. Prepare protective coating: add xylene to a stirring barrel according to the formula ratio, stir evenly at a constant temperature of 25 to 30 ° C for 5 to 10 minutes, and then add the second composite acrylic resin to the stirring barrel according to the ratio, stir while adding, and continue stirring for 30 to 60 minutes after adding to obtain a protective coating; S4. Production of scratch-resistant and wear-resistant silk-screen cold stamping gold foil: First, apply release coating on the base film layer and then dry it, then apply imaging coating on the release coating and then dry it, then vacuum-plate aluminum on the imaging coating, and finally apply protective coating on the aluminum layer and then dry it to form scratch-resistant and wear-resistant silk-screen cold stamping gold foil.

[0013] Furthermore, the preparation method of the first composite acrylic resin is as follows: 100 parts by mass of methanol, 1.7 parts by mass of antioxidant diphenylethylenediamine, and 10 parts by mass of the first acrylic resin copolymer were mixed and stirred at room temperature for 23 to 25 hours to obtain a first composite acrylic resin.

[0014] Furthermore, the preparation method of the first acrylic resin copolymer is as follows: 40 parts by mass of xylene are placed in a reaction container, and the temperature is raised to 84-86° C. while stirring. Subsequently, a mixture of 2.5 parts by mass of methyl methacrylate, 2-3 parts by mass of hydroxyethyl methacrylate, 2 parts by mass of butyl acrylate, 2-3 parts by mass of 3-allyl-2-hydroxybenzaldehyde, and 0.01-0.012 parts by mass of initiator azobisisobutyronitrile is added dropwise. After 3 hours, the addition is terminated, and the reaction is continued at the temperature for 3 hours to obtain the first acrylic resin copolymer.

[0015] Furthermore, the preparation method of the second composite acrylic resin is as follows: 40 parts by mass of xylene are placed in a reaction container, the temperature is raised to 69-72° C. while stirring, 10 parts by mass of the first acrylic resin copolymer, 0.16-0.48 parts by mass of hydroxy silicone oil, and 0.005 parts by mass of catalyst dibutyltin dilaurate are added, and the mixture is stirred for 4.8-5.2 hours to obtain the second composite acrylic resin.

[0016] Furthermore, the preparation method of the second acrylic resin copolymer is as follows: 40 parts by mass of xylene were placed in a reaction container, and the temperature was raised to 84-86° C. while stirring. Subsequently, a mixture of 2.5 parts by mass of methyl methacrylate, 2-3 parts by mass of hydroxyethyl methacrylate, 2 parts by mass of butyl acrylate, 2-3 parts by mass of silane coupling agent KH570, and 0.01-0.012 parts by mass of initiator azobisisobutyronitrile was added dropwise. The addition was stopped after 3 hours, and the reaction was continued by keeping the temperature for 3 hours to obtain the first acrylic resin copolymer.

[0017] By adopting the above technical solution, the present invention has the following beneficial effects: The scratch-resistant and wear-resistant silk-screen cold stamping gold foil of the present invention comprises a base film layer, a release coating coated on the base film layer, an imaging coating coated on the release coating, an aluminum layer plated on the imaging coating, and a protective coating coated on the aluminum layer; the base film layer adopts a PET film; the raw material components of the release coating include: an aqueous oxidized polyethylene wax emulsion; ethanol; water; the raw material components of the imaging coating include: a first composite acrylic resin, a coloring material, butanone, and ethyl acetate in parts by weight; the coloring material includes toner and copper-gold powder; the raw material components of the protective coating include: a second composite acrylic resin and xylene in parts by weight; the first composite acrylic resin is obtained by compounding a first acrylic resin copolymer and an antioxidant diphenylethylenediamine; the first acrylic resin copolymer is obtained by copolymerizing methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, and 3-allyl-2-hydroxybenzaldehyde; the second composite acrylic resin is obtained by compounding a second acrylic resin copolymer and hydroxy silicone oil; the second acrylic resin copolymer is obtained by compounding methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, and a silane coupling agent KH570.

[0018] Among them, the release layer uses water-based oxidized polyethylene wax emulsion as a release agent to adjust the tightness of the hot stamping and provide scratch and wear resistance. The surface of the release layer can withstand a scraping pressure of 6N~10N. The addition of ethanol and water can adjust the leveling of the release layer coating; the imaging coating uses the first composite acrylic resin to provide excellent molding performance and large-area hot stamping performance, so that the hot stamping pattern has a strong three-dimensional sense; the addition of coloring materials can provide color for the hot stamping powder; the protective coating uses the second composite acrylic resin to make the hot stamping foil have adhesion and bonding with the silk-screen cold stamping ink after heating and pressurizing, and at the same time provide the function of hot stamping fine sections.

[0019] The second acrylic resin copolymer of the present invention is grafted by copolymerization of methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate and silane coupling agent KH570, and then compounded with hydroxy silicone oil to form a polymer network with high crosslinking density of acrylic copolymer and silicone polymer molecular chains grafted to each other, thereby enhancing the mechanical properties and wear resistance of the protective coating.

[0020] The first acrylic resin copolymer of the present invention is copolymerized by methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate and 3-allyl-2-hydroxybenzaldehyde. A rigid benzene ring is introduced into the first acrylic resin copolymer to enhance the hardness and mechanical properties of the first acrylic resin copolymer. The first acrylic resin copolymer is then compounded with an antioxidant diphenylethylenediamine. The addition of the antioxidant can effectively improve the discoloration of the colorant due to oxidation. The aldehyde group in the first acrylic resin copolymer reacts with the amino group in the antioxidant to form a bis-Schiff base derivative ligand containing ONNO tetradentate coordination atoms. When the bis-Schiff base derivative ligand containing ONNO tetradentate coordination atoms is compounded with copper-gold powder to prepare an imaging coating, the copper-gold powder is uniformly dispersed in the imaging coating by the bis-Schiff base derivative ligand containing ONNO tetradentate coordination atoms in the first composite acrylic resin, thereby avoiding the reduction of mechanical properties of the imaging coating due to the agglomeration of the copper-gold powder, thereby avoiding the problem of the reduction of mechanical properties of the scratch-resistant and wear-resistant silk-screen cold stamping gold foil and the deterioration of gloss of the scratch-resistant and wear-resistant silk-screen cold stamping gold foil due to the poor leveling of the imaging coating due to the agglomeration of the copper-gold powder. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to make the content of the present invention more clearly understood, the present invention is further described in detail below according to specific embodiments and in conjunction with the accompanying drawings, wherein Figure 1 The schematic diagram is a structural diagram of a scratch-resistant and wear-resistant silk-screen cold stamping gold foil according to an embodiment of the present invention.

[0022] The numbers in the accompanying drawings are: base film layer 1, release coating 2, imaging coating 3, laser molding layer 4, aluminum layer 5, and protective coating 6. DETAILED DESCRIPTION

[0023] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with the accompanying drawings and specific implementation methods.

[0024] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Generally, the components of the embodiments of the present invention described and shown in the drawings here can be arranged and designed in various different configurations.

[0025] Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] The following embodiments are only used to more clearly illustrate the technical solutions of the present invention, and are not intended to limit the protection scope of the present invention.

[0027] (Overall Example) See Figure 1 , a scratch-resistant and wear-resistant silk-screen cold stamping gold foil, comprising a base film layer, a release coating coated on the base film layer, an imaging coating coated on the release coating, an aluminum layer plated on the imaging coating, and a protective coating coated on the aluminum layer; The raw material components of the imaging coating include, by weight: 40-60 parts by weight of a first composite acrylic resin, 0-4 parts by weight of a coloring material, 30-50 parts by weight of butanone, and 3-10 parts by weight of ethyl acetate; the coloring material includes 800-1200 mesh copper-gold powder and toner.

[0028] The base film is a PET film.

[0029] The release coating comprises, by weight, 5 to 10 parts by weight of aqueous oxidized polyethylene wax emulsion; 50 to 60 parts by weight of ethanol; and 30 to 40 parts by weight of water.

[0030] The raw material components of the protective coating include, by weight: 60-80 parts by weight of the second composite acrylic resin and 20-40 parts by weight of xylene.

[0031] The first composite acrylic resin is obtained by compounding a first acrylic resin copolymer and an antioxidant diphenylethylenediamine; the first acrylic resin copolymer is obtained by copolymerizing methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate and 3-allyl-2-hydroxybenzaldehyde.

[0032] The second composite acrylic resin is obtained by compounding a second acrylic resin copolymer and hydroxy silicone oil; The second acrylic resin copolymer is composed of methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate and silane coupling agent KH570.

[0033] In a further embodiment, the imaging coating and the aluminum layer may also be provided with a laser embossing layer 4, which is obtained by laser embossing on the imaging coating.

[0034] The present invention also provides a preparation process of a scratch-resistant and wear-resistant silk-screen cold stamping gold foil, comprising the following preparation steps: S1. Prepare release coating: add ethanol and water into a stirring barrel according to the formula ratio, stir evenly at a constant temperature of 25~30°C for 5~15min, then add the aqueous oxidized polyethylene wax emulsion into the stirring barrel according to the proportion, stir while adding, and continue stirring for 30~60min after adding to obtain the release coating; S2. Prepare an imaging coating: add butanone to a stirring barrel according to the formula ratio, stir evenly at a constant temperature of 25 to 30 ° C for 5 to 15 minutes, and then add ethyl acetate, a first composite acrylic resin, and a coloring material to a stirring barrel in proportion, stirring while adding, and continue stirring for 23 to 25 hours after adding to obtain an imaging coating; S3. Prepare protective coating: add xylene to a stirring barrel according to the formula ratio, stir evenly at a constant temperature of 25 to 30 ° C for 5 to 10 minutes, and then add the second composite acrylic resin to the stirring barrel according to the ratio, stir while adding, and continue stirring for 30 to 60 minutes after adding to obtain a protective coating; S4. Production of scratch-resistant and wear-resistant silk screen cold stamping gold foil: First apply the release coating on the base film layer and then dry it to a dry weight of 0.04g / m 2 ~0.08g / m 2 Then apply the imaging coating on the release coating and dry it to a dry weight of 0.9g / m 2 ~1.1g / m 2 Then, vacuum aluminum is plated on the imaging coating with a thickness of 30-32 nm. Finally, a protective coating is applied on the aluminum layer and then dried to a dry weight of 0.6 g / m 2 ~0.8g / m 2 , forming a scratch-resistant and wear-resistant silk-screen cold stamping gold foil.

[0035] The preparation method of the first composite acrylic resin is as follows: 100 parts by mass of methanol, 1.7 parts by mass of antioxidant diphenylethylenediamine, and 10 parts by mass of the first acrylic resin copolymer were mixed and stirred at room temperature for 23 to 25 hours to obtain a first composite acrylic resin.

[0036] The preparation method of the first acrylic resin copolymer is as follows: 40 parts by mass of xylene are placed in a reaction container, and the temperature is raised to 84-86° C. while stirring. Subsequently, a mixture of 2.5 parts by mass of methyl methacrylate, 2-3 parts by mass of hydroxyethyl methacrylate, 2 parts by mass of butyl acrylate, 2-3 parts by mass of 3-allyl-2-hydroxybenzaldehyde, and 0.01-0.012 parts by mass of initiator azobisisobutyronitrile is added dropwise. After 3 hours, the addition is terminated, and the reaction is continued at the temperature for 3 hours to obtain the first acrylic resin copolymer.

[0037] Furthermore, the preparation method of the second composite acrylic resin is as follows: 40 parts by mass of xylene are placed in a reaction container, the temperature is raised to 69-72° C. while stirring, 10 parts by mass of the first acrylic resin copolymer, 0.16-0.48 parts by mass of hydroxy silicone oil, and 0.005 parts by mass of catalyst dibutyltin dilaurate are added, and the mixture is stirred for 4.8-5.2 hours to obtain the second composite acrylic resin.

[0038] The preparation method of the second acrylic resin copolymer is as follows: 40 parts by mass of xylene were placed in a reaction container, and the temperature was raised to 84-86° C. while stirring. Subsequently, a mixture of 2.5 parts by mass of methyl methacrylate, 2-3 parts by mass of hydroxyethyl methacrylate, 2 parts by mass of butyl acrylate, 2-3 parts by mass of silane coupling agent KH570, and 0.01-0.012 parts by mass of initiator azobisisobutyronitrile was added dropwise. The addition was stopped after 3 hours, and the reaction was continued by keeping the temperature for 3 hours to obtain the first acrylic resin copolymer.

[0039] (Example 1) A preparation process of a scratch-resistant and wear-resistant silk-screen cold stamping gold foil, comprising the following preparation steps: S1. Prepare ingredients according to the following raw materials and components: The raw material components of the imaging coating include, by weight: 40 parts by weight of a first composite acrylic resin, 1 part by weight of 800-mesh copper-gold powder, 30 parts by weight of butanone, and 3 parts by weight of ethyl acetate; The raw material components of the release coating include, by weight: 5 parts by weight of aqueous oxidized polyethylene wax emulsion, 50 parts by weight of ethanol, and 30 parts by weight of water; The raw material components of the protective coating layer include, by weight: 60 parts by weight of the second composite acrylic resin and 20 parts by weight of xylene.

[0040] S2. Preparation of release coating: Add ethanol and water to a stirring barrel according to the formula ratio, stir evenly at a constant temperature of 25 ° C for 5 minutes, then add the aqueous oxidized polyethylene wax emulsion to the stirring barrel according to the proportion, stir while adding, and continue stirring for 30 minutes after adding to obtain a release coating; S3. Prepared imaging coating: butanone was added to a stirring barrel according to the formula ratio, stirred evenly at a constant temperature of 25 ° C for 5 min, and then ethyl acetate, a first composite acrylic resin, and copper powder were added to a stirring barrel in accordance with the ratio, stirred while adding, and continued stirring for 23 h after adding to obtain an imaging coating; S4 preparation of protective coating: xylene was added to a stirring barrel according to the formula ratio, stirred evenly at a constant temperature of 25 ° C for 5min, and then the second composite acrylic resin was added to the stirring barrel according to the ratio, stirred while adding, and continued stirring for 30min after adding to obtain a protective coating; S5. Production of scratch-resistant and wear-resistant silk-screen cold stamping gold foil: First, apply release coating on the base film layer and then dry it, then apply imaging coating on the release coating and then dry it, then vacuum-plate aluminum on the imaging coating, and finally apply protective coating on the aluminum layer and then dry it to form scratch-resistant and wear-resistant silk-screen cold stamping gold foil.

[0041] The preparation method of the first composite acrylic resin is as follows: 100 parts by mass of methanol, 1.7 parts by mass of antioxidant diphenylethylenediamine, and 10 parts by mass of the first acrylic resin copolymer are mixed and stirred at room temperature for 23 hours to obtain the first composite acrylic resin.

[0042] The preparation method of the first acrylic resin copolymer is as follows: 40 parts by mass of xylene are placed in a reaction container, the temperature is raised to 84° C. while stirring, and then a mixture of 2.5 parts by mass of methyl methacrylate, 2 parts by mass of hydroxyethyl methacrylate, 2 parts by mass of butyl acrylate, 2 parts by mass of 3-allyl-2-hydroxybenzaldehyde, and 0.01 parts by mass of initiator azobisisobutyronitrile is added dropwise, the addition is terminated after 3 hours, and the reaction is kept warm for 3 hours to obtain the first acrylic resin copolymer.

[0043] The preparation method of the second composite acrylic resin is as follows: 40 parts by weight of xylene are placed in a reaction container, the temperature is raised to 69° C. while stirring, 10 parts by weight of the first acrylic resin copolymer, 0.16 parts by weight of hydroxy silicone oil, and 0.005 parts by weight of catalyst dibutyltin dilaurate are added, and the mixture is stirred for 4.8 hours to obtain the second composite acrylic resin.

[0044] The preparation method of the second acrylic resin copolymer is as follows: 40 parts by mass of xylene are placed in a reaction container, the temperature is raised to 84° C. while stirring, and then a mixture of 2.5 parts by mass of methyl methacrylate, 2 parts by mass of hydroxyethyl methacrylate, 2 parts by mass of butyl acrylate, 2 parts by mass of silane coupling agent KH570, and 0.01 parts by mass of initiator azobisisobutyronitrile is added dropwise, the addition is stopped after 3 hours, and the reaction is kept warm for 3 hours to obtain the first acrylic resin copolymer.

[0045] (Example 2) A preparation process of a scratch-resistant and wear-resistant silk-screen cold stamping gold foil, comprising the following preparation steps: S1. Prepare ingredients according to the following raw materials and components: The raw material components of the imaging coating include, by weight: 50 parts by weight of a first composite acrylic resin, 3 parts by weight of 1000-mesh copper-gold powder, 40 parts by weight of butanone, and 6 parts by weight of ethyl acetate; The raw material components of the release coating include, by weight: 8 parts by weight of aqueous oxidized polyethylene wax emulsion, 55 parts by weight of ethanol, and 35 parts by weight of water; The raw material components of the protective coating layer include, by weight: 70 parts by weight of the second composite acrylic resin and 30 parts by weight of xylene.

[0046] S2. Preparation of release coating: Add ethanol and water to a stirring barrel according to the formula ratio, stir evenly at a constant temperature of 28 ° C for 10 minutes, then add the aqueous oxidized polyethylene wax emulsion to the stirring barrel according to the proportion, stir while adding, and continue stirring for 45 minutes after adding to obtain a release coating; S3. Prepared imaging coating: butanone was added to a stirring barrel according to the formula ratio, stirred evenly at a constant temperature of 28 ° C for 10 min, and then ethyl acetate, a first composite acrylic resin, and copper powder were added to a stirring barrel in accordance with the proportion, stirred while adding, and continued stirring for 24 h after adding to obtain an imaging coating; S4 preparation of protective coating: xylene was added to a stirring barrel according to the formula ratio, stirred evenly at a constant temperature of 28 ° C for 8min, and then the second composite acrylic resin was added to the stirring barrel according to the ratio, stirred while adding, and continued stirring for 45min after adding to obtain a protective coating; S5. Production of scratch-resistant and wear-resistant silk-screen cold stamping gold foil: First, apply release coating on the base film layer and then dry it, then apply imaging coating on the release coating and then dry it, then vacuum-plate aluminum on the imaging coating, and finally apply protective coating on the aluminum layer and then dry it to form scratch-resistant and wear-resistant silk-screen cold stamping gold foil.

[0047] The preparation method of the first composite acrylic resin is as follows: 100 parts by mass of methanol, 1.7 parts by mass of antioxidant diphenylethylenediamine, and 10 parts by mass of the first acrylic resin copolymer are mixed and stirred at room temperature for 24 hours to obtain the first composite acrylic resin.

[0048] The preparation method of the first acrylic resin copolymer is as follows: 40 parts by mass of xylene are placed in a reaction container, the temperature is raised to 85° C. while stirring, and then a mixture of 2.5 parts by mass of methyl methacrylate, 2.5 parts by mass of hydroxyethyl methacrylate, 2 parts by mass of butyl acrylate, 2.5 parts by mass of 3-allyl-2-hydroxybenzaldehyde, and 0.011 parts by mass of initiator azobisisobutyronitrile is added dropwise, the addition is terminated after 3 hours, and the reaction is kept warm for 3 hours to obtain the first acrylic resin copolymer.

[0049] The preparation method of the second composite acrylic resin is as follows: 40 parts by mass of xylene are placed in a reaction container, the temperature is raised to 71° C. while stirring, 10 parts by mass of the first acrylic resin copolymer, 0.32 parts by mass of hydroxy silicone oil, and 0.005 parts by mass of catalyst dibutyltin dilaurate are added, and the mixture is stirred for 5 hours to obtain the second composite acrylic resin.

[0050] The preparation method of the second acrylic resin copolymer is as follows: 40 parts by mass of xylene are placed in a reaction container, the temperature is raised to 85° C. while stirring, and then a mixture of 2.5 parts by mass of methyl methacrylate, 2.5 parts by mass of hydroxyethyl methacrylate, 2 parts by mass of butyl acrylate, 2.5 parts by mass of silane coupling agent KH570, and 0.011 parts by mass of initiator azobisisobutyronitrile is added dropwise, the addition is stopped after 3 hours, and the reaction is kept warm for 3 hours to obtain the first acrylic resin copolymer.

[0051] (Example 3) A preparation process of a scratch-resistant and wear-resistant silk-screen cold stamping gold foil, comprising the following preparation steps: S1. Prepare ingredients according to the following raw materials and components: The raw material components of the imaging coating include, by weight: 60 parts by weight of a first composite acrylic resin, 4 parts by weight of 1200-mesh copper-gold powder, 50 parts by weight of butanone, and 10 parts by weight of ethyl acetate; The raw material components of the release coating include, by weight: 10 parts by weight of aqueous oxidized polyethylene wax emulsion, 60 parts by weight of ethanol, and 40 parts by weight of water; The raw material components of the protective coating layer include, by weight: 80 parts by weight of the second composite acrylic resin and 40 parts by weight of xylene.

[0052] S2. Preparation of release coating: Add ethanol and water to a stirring barrel according to the formula ratio, stir evenly at a constant temperature of 30 ° C for 15 minutes, then add the aqueous oxidized polyethylene wax emulsion to the stirring barrel according to the proportion, stir while adding, and continue stirring for 60 minutes after adding to obtain a release coating; S3. Prepared imaging coating: butanone was added to a stirring barrel according to the formula ratio, stirred evenly at a constant temperature of 30 ° C for 15 min, and then ethyl acetate, a first composite acrylic resin, and copper powder were added to a stirring barrel in accordance with the proportion, stirred while adding, and continued stirring for 25 h after adding to obtain an imaging coating; S4 preparation of protective coating: xylene was added to a stirring barrel according to the formula ratio, stirred evenly at a constant temperature of 30 ° C for 10min, and then the second composite acrylic resin was added to the stirring barrel according to the ratio, stirred while adding, and continued stirring for 60min after adding to obtain a protective coating; S5. Production of scratch-resistant and wear-resistant silk-screen cold stamping gold foil: First, apply release coating on the base film layer and then dry it, then apply imaging coating on the release coating and then dry it, then vacuum-plate aluminum on the imaging coating, and finally apply protective coating on the aluminum layer and then dry it to form scratch-resistant and wear-resistant silk-screen cold stamping gold foil.

[0053] The preparation method of the first composite acrylic resin is as follows: 100 parts by mass of methanol, 1.7 parts by mass of antioxidant diphenylethylenediamine, and 10 parts by mass of the first acrylic resin copolymer are mixed and stirred at room temperature for 25 hours to obtain the first composite acrylic resin.

[0054] The preparation method of the first acrylic resin copolymer is as follows: 40 parts by mass of xylene are placed in a reaction container, the temperature is raised to 86° C. while stirring, and then a mixture of 2.5 parts by mass of methyl methacrylate, 3 parts by mass of hydroxyethyl methacrylate, 2 parts by mass of butyl acrylate, 3 parts by mass of 3-allyl-2-hydroxybenzaldehyde, and 0.012 parts by mass of initiator azobisisobutyronitrile is added dropwise, the addition is stopped after 3 hours, and the reaction is kept warm for 3 hours to obtain the first acrylic resin copolymer.

[0055] The preparation method of the second composite acrylic resin is as follows: 40 parts by weight of xylene are placed in a reaction container, the temperature is raised to 72° C. while stirring, 10 parts by weight of the first acrylic resin copolymer, 0.48 parts by weight of hydroxy silicone oil, and 0.005 parts by weight of catalyst dibutyltin dilaurate are added, and the mixture is stirred for 5.2 hours to obtain the second composite acrylic resin.

[0056] The preparation method of the second acrylic resin copolymer is as follows: 40 parts by mass of xylene are placed in a reaction container, the temperature is raised to 86° C. while stirring, and then a mixture of 2.5 parts by mass of methyl methacrylate, 3 parts by mass of hydroxyethyl methacrylate, 2 parts by mass of butyl acrylate, 3 parts by mass of silane coupling agent KH570, and 0.012 parts by mass of initiator azobisisobutyronitrile is added dropwise, the addition is stopped after 3 hours, and the reaction is kept warm for 3 hours to obtain a first acrylic resin copolymer.

[0057] (Example 2) A preparation process of a scratch-resistant and wear-resistant silk-screen cold stamping gold foil, comprising the following preparation steps: S1. Prepare ingredients according to the following raw materials and components: The raw material components of the imaging coating include, by weight: 50 parts by weight of a first composite acrylic resin, 3 parts by weight of a toner (model: Aotelai 603), 40 parts by weight of butanone, and 6 parts by weight of ethyl acetate; The raw material components of the release coating include, by weight: 8 parts by weight of aqueous oxidized polyethylene wax emulsion, 55 parts by weight of ethanol, and 35 parts by weight of water; The raw material components of the protective coating layer include, by weight: 70 parts by weight of the second composite acrylic resin and 30 parts by weight of xylene.

[0058] S2. Preparation of release coating: Add ethanol and water to a stirring barrel according to the formula ratio, stir evenly at a constant temperature of 28 ° C for 10 minutes, then add the aqueous oxidized polyethylene wax emulsion to the stirring barrel according to the proportion, stir while adding, and continue stirring for 45 minutes after adding to obtain a release coating; S3. Prepared imaging coating: butanone was added to a stirring barrel according to the formula ratio, stirred evenly at a constant temperature of 28 ° C for 10 min, and then ethyl acetate, a first composite acrylic resin, and toner were added to a stirring barrel in order according to the ratio, stirred while adding, and continued stirring for 24 h after adding to obtain an imaging coating; S4 preparation of protective coating: xylene was added to a stirring barrel according to the formula ratio, stirred evenly at a constant temperature of 28 ° C for 8min, and then the second composite acrylic resin was added to the stirring barrel according to the ratio, stirred while adding, and continued stirring for 45min after adding to obtain a protective coating; S5. Production of scratch-resistant and wear-resistant silk-screen cold stamping gold foil: First, apply release coating on the base film layer and then dry it, then apply imaging coating on the release coating and then dry it, then vacuum-plate aluminum on the imaging coating, and finally apply protective coating on the aluminum layer and then dry it to form scratch-resistant and wear-resistant silk-screen cold stamping gold foil.

[0059] The preparation method of the first composite acrylic resin is as follows: 100 parts by mass of methanol, 1.7 parts by mass of antioxidant diphenylethylenediamine, and 10 parts by mass of the first acrylic resin copolymer are mixed and stirred at room temperature for 24 hours to obtain the first composite acrylic resin.

[0060] The preparation method of the first acrylic resin copolymer is as follows: 40 parts by mass of xylene are placed in a reaction container, the temperature is raised to 85° C. while stirring, and then a mixture of 2.5 parts by mass of methyl methacrylate, 2.5 parts by mass of hydroxyethyl methacrylate, 2 parts by mass of butyl acrylate, 2.5 parts by mass of 3-allyl-2-hydroxybenzaldehyde, and 0.011 parts by mass of initiator azobisisobutyronitrile is added dropwise, the addition is terminated after 3 hours, and the reaction is kept warm for 3 hours to obtain the first acrylic resin copolymer.

[0061] The preparation method of the second composite acrylic resin is as follows: 40 parts by mass of xylene are placed in a reaction container, the temperature is raised to 71° C. while stirring, 10 parts by mass of the first acrylic resin copolymer, 0.32 parts by mass of hydroxy silicone oil, and 0.005 parts by mass of catalyst dibutyltin dilaurate are added, and the mixture is stirred for 5 hours to obtain the second composite acrylic resin.

[0062] The preparation method of the second acrylic resin copolymer is as follows: 40 parts by mass of xylene are placed in a reaction container, the temperature is raised to 85° C. while stirring, and then a mixture of 2.5 parts by mass of methyl methacrylate, 2.5 parts by mass of hydroxyethyl methacrylate, 2 parts by mass of butyl acrylate, 2.5 parts by mass of silane coupling agent KH570, and 0.011 parts by mass of initiator azobisisobutyronitrile is added dropwise, the addition is stopped after 3 hours, and the reaction is kept warm for 3 hours to obtain the first acrylic resin copolymer.

[0063] Comparative Example 1 The only difference between Comparative Example 1 and Example 2 is that the first acrylic resin copolymer is obtained by copolymerizing only methyl methacrylate, hydroxyethyl methacrylate and butyl acrylate; the remaining steps and components are the same as those in Example 2.

[0064] Comparative Example 2 The difference between Comparative Example 2 and Example 2 is that the antioxidant of the first composite acrylic resin is 1010; the remaining steps and components are the same as those of Example 2.

[0065] Comparative Example 3 The only difference between Comparative Example 3 and Example 2 is that the second acrylic resin copolymer is obtained by copolymerizing only methyl methacrylate, hydroxyethyl methacrylate and butyl acrylate; the remaining steps and components are the same as those in Example 2.

[0066] Comparative Example 4 The only difference between Comparative Example 4 and Example 2 is that the second composite acrylic resin is a second acrylic resin copolymer; the remaining steps and components are the same as those of Example 2.

[0067] Effect example: Tensile property test: The scratch-resistant and wear-resistant silk-screen cold stamping gold foil prepared in the examples and comparative examples were tested for tensile properties according to GB / T228.1.

[0068] Glossiness: The scratch-resistant and wear-resistant silk-screen cold stamping gold foil prepared in the examples and comparative examples was tested for glossiness at an incident angle of 60°.

[0069] Wear resistance: The scratch-resistant and wear-resistant silk-screen cold stamping gold foil prepared in the examples and comparative examples was tested for film hardness according to GB / T6379.

[0070] Table 1 Pencil hardness Tensile strength (MPa) Glossiness (GU) Example 1 H 14.11 92 Example 2 H 14.31 96 Example 3 H 14.24 94 Example 4 H 14.32 90 Comparative Example 1 B 12.11 80 Comparative Example 2 HB 13.98 76 Comparative Example 3 HB 11.31 95 Comparative Example 4 HB 13.46 92 Table 1 below shows the performance test results of the scratch-resistant and wear-resistant silk-screen cold stamping gold foils prepared in the examples and comparative examples: Referring to Table 1, compared with Examples 1-4 and Comparative Examples 1-4, the silk-screen cold stamping gold foil prepared by the Examples has better wear resistance, mechanical properties and higher gloss; compared with Example 2, Comparative Examples 1-2 use 3-allyl-2-hydroxybenzaldehyde to prepare a first acrylic resin copolymer and an antioxidant diphenylethylenediamine to obtain a first composite acrylic resin, and the silk-screen cold stamping gold foil prepared has better wear resistance, mechanical properties and higher gloss; compared with Example 2, Comparative Examples 1-2 use silane coupling agent KH570 to prepare a second acrylic resin copolymer and hydroxy silicone oil to obtain a second composite acrylic resin, and the silk-screen cold stamping gold foil prepared has better wear resistance and mechanical properties.

[0071] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A scratch-resistant and wear-resistant silk screen cold stamping gold foil. It is characterized in that It comprises a base film layer (1), a release coating (2) coated on the base film layer (1), an imaging coating (3) coated on the release coating (2), an aluminum layer (5) plated on the imaging coating (3), and a protective coating (6) coated on the aluminum layer (5); The imaging coating (3) comprises, by weight, 40 to 60 parts by weight of a first composite acrylic resin, 0 to 4 parts by weight of a coloring material, 30 to 50 parts by weight of butanone, and 3 to 10 parts by weight of ethyl acetate; The coloring material includes toner and copper-gold powder.

2. The scratch-resistant and wear-resistant silk-screen cold stamping gold foil according to claim 1, It is characterized in that The release coating (2) comprises, by weight, raw material components: 5 to 10 parts by weight of aqueous oxidized polyethylene wax emulsion E-842N; 50 to 60 parts by weight of ethanol; and 30 to 40 parts by weight of water.

3. The scratch-resistant and wear-resistant silk-screen cold stamping gold foil according to claim 2, It is characterized in that The protective coating (6) comprises, by weight, 60 to 80 parts by weight of a second composite acrylic resin and 20 to 40 parts by weight of xylene.

4. The scratch-resistant and wear-resistant silk-screen cold stamping gold foil according to claim 1, It is characterized in that The first composite acrylic resin is obtained by compounding a first acrylic resin copolymer and an antioxidant diphenylethylenediamine; the first acrylic resin copolymer is obtained by copolymerizing methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate and 3-allyl-2-hydroxybenzaldehyde.

5. The scratch-resistant and wear-resistant silk-screen cold stamping gold foil according to claim 1, It is characterized in that The second composite acrylic resin is obtained by compounding a second acrylic resin copolymer and hydroxy silicone oil; The second acrylic resin copolymer is composed of methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate and silane coupling agent KH570.

6. A process for preparing the scratch-resistant and wear-resistant silk-screen cold stamping gold foil according to any one of claims 1 to 5, It is characterized in that The method comprises the following preparation steps: S1. Prepare the release coating (2) coating: add ethanol and water according to the formula ratio into a stirring bucket, stir evenly at a constant temperature of 25-30°C for 5-15 minutes, then add the aqueous oxidized polyethylene wax emulsion into the stirring bucket according to the proportion, stir while adding, and continue stirring for 30-60 minutes after adding to obtain the release coating (2) coating; S2. Prepare imaging coating (3) coating: add butanone to a stirring barrel according to the formula ratio, stir evenly at a constant temperature of 25~30°C for 5~15min, then add ethyl acetate, the first composite acrylic resin, and the coloring material to the stirring barrel in order according to the ratio, stir while adding, and continue stirring for 23~25h after adding to obtain imaging coating (3) coating; S3. Preparation of protective coating (6) coating: xylene is added to a stirring barrel according to the formula ratio, and stirred evenly at a constant temperature of 25 to 30 ° C for 5 to 10 minutes, and then the second composite acrylic resin is added to the stirring barrel according to the proportion, stirring while adding, and stirring is continued for 30 to 60 minutes after the addition to obtain a protective coating (6) coating; S4. Production of scratch-resistant and wear-resistant silk-screen cold stamping gold foil: First, a release coating (2) is applied on the base film layer (1) and then dried, then an imaging coating (3) is applied on the release coating (2) and then dried, then vacuum aluminum is plated on the imaging coating (3), and finally a protective coating (6) is applied on the aluminum layer (5) and then dried to form a scratch-resistant and wear-resistant silk-screen cold stamping gold foil.

7. The preparation process of the scratch-resistant and wear-resistant silk-screen cold stamping gold foil according to claim 1, It is characterized in that The preparation method of the first composite acrylic resin is as follows: 100 parts by mass of methanol, 1.7 parts by mass of antioxidant diphenylethylenediamine, and 10 parts by mass of the first acrylic resin copolymer were mixed and stirred at room temperature for 23 to 25 hours to obtain a first composite acrylic resin.

8. The process for preparing the scratch-resistant and wear-resistant silk-screen cold stamping gold foil according to claim 7, It is characterized in that The preparation method of the first acrylic resin copolymer is as follows: 40 parts by mass of xylene are placed in a reaction container, and the temperature is raised to 84-86° C. while stirring. Subsequently, a mixture of 2.5 parts by mass of methyl methacrylate, 2-3 parts by mass of hydroxyethyl methacrylate, 2 parts by mass of butyl acrylate, 2-3 parts by mass of 3-allyl-2-hydroxybenzaldehyde, and 0.01-0.012 parts by mass of initiator azobisisobutyronitrile is added dropwise. After 3 hours, the addition is terminated, and the reaction is continued at the temperature for 3 hours to obtain the first acrylic resin copolymer.

9. The process for preparing the scratch-resistant and wear-resistant silk-screen cold stamping gold foil according to claim 1, It is characterized in that The preparation method of the second composite acrylic resin is as follows: 40 parts by weight of xylene are placed in a reaction container, the temperature is raised to 69-72° C. while stirring, 10 parts by weight of the first acrylic resin copolymer, 0.16-0.48 parts by weight of hydroxy silicone oil, and 0.005 parts by weight of catalyst dibutyltin dilaurate are added, and the mixture is stirred for 4.8-5.2 hours to obtain the second composite acrylic resin.

10. The process for preparing the scratch-resistant and wear-resistant silk-screen cold stamping gold foil according to claim 9, It is characterized in that The preparation method of the second acrylic resin copolymer is as follows: 40 parts by mass of xylene were placed in a reaction container, and the temperature was raised to 84-86° C. while stirring. Subsequently, a mixture of 2.5 parts by mass of methyl methacrylate, 2-3 parts by mass of hydroxyethyl methacrylate, 2 parts by mass of butyl acrylate, 2-3 parts by mass of silane coupling agent KH570, and 0.01-0.012 parts by mass of initiator azobisisobutyronitrile was added dropwise. The addition was stopped after 3 hours, and the reaction was continued by keeping the temperature for 3 hours to obtain the first acrylic resin copolymer.

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