Thin offset printing and cold stamping material and preparation process thereof

Abstract

The invention discloses a thin offset printing cold stamping material and a preparation process thereof, and belongs to the technical field of cold stamping materials. The thin offset printing and cold stamping material comprises a base film layer, a release layer coated on the base film layer, an imaging layer coated on the release layer, an aluminum-plated layer plated on the imaging layer, and a protective glue layer coated on the aluminum-plated layer, the imaging layer comprises the following raw material components: butanone, ethyl acetate, an imaging layer resin base material and toner; the resin base material of the imaging layer is obtained by copolymerizing methyl methacrylate, hydroxyethyl methylacrylate, an unsaturated stabilizer tri (allylbenzene) imidazoline and 2, 4, 6-tri (2-allylphenoxy)-1, 3, 5-triazine, and the resin base material of the imaging layer is obtained by copolymerizing methyl methacrylate, hydroxyethyl methylacrylate, an unsaturated stabilizer tri (allylbenzene) imidazoline and 2, 4, 6-tri (2-allylphenoxy)-1, 3, 5-triazine; the release layer is prepared from the following raw material components: ethyl orthosilicate, octaphenyl cyclotetrasiloxane, tetravinyl tetramethyl cyclotetrasiloxane, a dimethyl siloxane mixed ring body, n-heptane and 3, 5-di-tert-butyl salicylaldehyde; the protective adhesive layer comprises methyl methacrylate, hydroxyethyl methylacrylate, butyl acrylate, xylene and glycidyl acrylate.

Description

Technical Field

[0001] The invention relates to the technical field of cold stamping materials, in particular to a thin offset cold stamping material and a preparation process thereof. Background Art

[0002] With the rapid development of the packaging and printing industry, the market demand for cold foil materials continues to increase. Cold foil materials are favored for their unique decorative effects and wide applications.

[0003] However, traditional cold stamping materials have insufficient bonding strength between the release layer, imaging layer and aluminized layer, mainly due to the large differences in the interface characteristics of each layer and the lack of effective chemical bonding or physical interlocking. For example, although the release layer made of silicon-based materials has good demoulding properties, it also leads to weak bonding strength with other layers.

[0004] In addition, in order to achieve rich color effects, the toner added to the imaging layer will change its surface properties and internal structure, thereby affecting the adhesion with the release layer and the aluminum coating layer. The toner particles may form defect points on the interface, reducing the contact area and reducing the overall adhesion strength. The roughness of the imaging layer surface also directly affects the appearance quality of the product. If the surface is not smooth enough, the aluminum coating layer cannot be evenly covered during deposition, resulting in a decrease in glossiness. At the same time, these tiny bumps may also become stress concentration points in subsequent use, affecting the durability of the material.

[0005] Therefore, the present invention solves the above-mentioned problem by preparing a thin offset cold stamping material. Summary of the invention

[0006] The purpose of the present invention is to provide a thin offset cold foil material and a preparation process thereof, so as to solve the technical problems mentioned in the above background technology.

[0007] The technical solution for achieving the purpose of the present invention is: A thin offset cold stamping material comprises a base film layer, a release layer coated on the base film layer, an imaging layer coated on the release layer, an aluminum coating layer vacuum-evaporated on the imaging layer, and a protective adhesive layer coated on the aluminum coating layer; the base film layer adopts a 6U BOPET film.

[0008] Furthermore, the release layer raw material components include: tetraethyl orthosilicate, octaphenylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane, dimethylsiloxane mixed ring body, n-heptane, 3,5-di-tert-butyl salicylaldehyde, tris(trimethylsilyl)phosphate, and polydimethylsiloxane.

[0009] Furthermore, the imaging layer comprises, by weight, 30 to 50 parts of butanone, 5 to 10 parts of ethyl acetate, 40 to 60 parts of an imaging layer resin base material, and 1 to 3 parts of toner; the imaging layer resin base comprises, by weight, 2.5 parts of methyl methacrylate, 2 to 3 parts of hydroxyethyl methacrylate, 2 parts of 2,4,6-tris(2-allylphenoxy)-1,3,5-triazine, 2 to 4 parts of an unsaturated stabilizer, 0.01 to 0.012 parts of an initiator, and 40 parts of xylene.

[0010] Furthermore, the raw material components of the protective rubber layer include, by weight: 60 to 80 parts by weight of a protective layer resin base material and 20 to 40 parts by weight of xylene; the raw material components of the protective layer resin base material include, by weight: 2.5 parts by weight of methyl methacrylate, 2 to 3 parts by weight of hydroxyethyl methacrylate, 2 parts by weight of butyl acrylate, 2 to 4 parts by weight of glycidyl acrylate, 0.01 to 0.012 parts by weight of an initiator and 40 parts by weight of xylene.

[0011] Furthermore, before vacuum aluminum plating, the imaging layer is ultrasonically immersed in an aluminum acetate mixed solution and a hydrogen bromide aqueous solution in sequence; wherein the aluminum acetate mixed solution comprises, by weight, 50 parts by weight of ethanol, 50 parts by weight of acetic anhydride, 2 to 4 parts by weight of aluminum acetate, and 1.6 to 1.7 parts by weight of sodium ethoxide.

[0012] The present invention also provides a preparation process of a thin offset cold stamping material, comprising the following preparation steps: (1) preparing a release layer coating; (2) Preparation of imaging layer coating: Add butanone into a stirring bucket according to the formula ratio, stir evenly at a constant temperature of 25-30°C for 5-15 minutes, then add ethyl acetate, imaging layer resin base material, and color powder into the stirring bucket in order according to the proportion, stirring while adding, and continue stirring for 23-25 ​​hours after adding, to obtain the imaging coating; (3) Preparation of protective coating: Add xylene into a stirring barrel according to the formula ratio, stir evenly at a constant temperature of 25-30°C for 5-10 minutes, then add the protective layer resin base material into the stirring barrel according to the proportion, stirring while adding, and continue stirring for 30-60 minutes after adding to obtain the protective coating; (4) First, a release coating is applied on the base film layer and then dried. Then, an imaging layer is applied on the release coating and then dried. Subsequently, the layer is immersed in 100 parts by weight of an aluminum acetate mixture and heated to 135-145° C. for ultrasonic immersion for 7-9 hours. Subsequently, 11-12 parts by weight of a 40% aqueous hydrogen bromide solution is added and ultrasonic immersion is continued for 4 hours. After being taken out, the layer is placed in 10 parts by weight of methanol and ultrasonic immersion is continued at room temperature for 24 hours. After being taken out and dried, vacuum aluminum is plated on the immersed imaging layer. Finally, a protective coating is applied on the aluminum-plated layer and then dried to form a thin offset cold stamping material.

[0013] Furthermore, the preparation method of the release layer coating is as follows: 75 to 80 parts by weight of a dimethylsiloxane mixed ring body is placed in a 50°C reactor, dehydrated for 28 to 32 minutes under a nitrogen atmosphere and -0.095 MPa, then 15 parts by weight of tetravinyltetramethylcyclotetrasiloxane, 5 to 15 parts by weight of octaphenylcyclotetrasiloxane and 150 ppm of a catalyst methanol potassium alkali glue are added, and dehydration is continued for 28 to 32 minutes under a nitrogen atmosphere and -0.095 MPa, then the temperature is raised to 170°C, reacted for 80 to 100 minutes, naturally cooled to room temperature, and then 0.0003 parts by weight of tris(trimethylsilyl) phosphate is added, stirred at room temperature for 28 to 30 minutes, and then the unreacted monomers are recovered under reduced pressure under a 200°C nitrogen atmosphere and -0.095 MPa conditions, then the temperature is lowered to 90°C, 20 ppm of chloroplatinic acid catalyst is added, and the reaction is continued at a constant temperature for 4 h and then cooled to room temperature, 40-50 parts by weight of polydimethylsiloxane, 5-15 parts by weight of 3,5-di-tert-butyl salicylaldehyde and 50-60 parts by weight of n-heptane were added to obtain a release layer coating.

[0014] Furthermore, the preparation method of the catalyst potassium methoxide gel is as follows: 20 parts by mass of a dimethylsiloxane mixed ring body is placed in a 50°C reactor, and water is removed for 28 to 32 minutes under a nitrogen atmosphere and -0.095MPa conditions, and then 0.3 parts by mass of potassium methoxide is quickly added to continue to remove water for 28 to 32 minutes under a nitrogen atmosphere and -0.095MPa conditions, and then the temperature is raised to 110°C, and the reaction is carried out at an appropriate stirring rate for 2 hours to obtain potassium methoxide gel, which is filled with nitrogen and stored at a low temperature for later use.

[0015] Furthermore, the preparation method of the imaging layer resin base material is as follows: 40 parts by mass of xylene are placed in a reaction container, the temperature is raised to 84-86° C. while stirring, and then a mixture of 2.5 parts by mass of methyl methacrylate, 2-3 parts by mass of hydroxyethyl methacrylate, 2 parts by mass of 2,4,6-tris(2-allylphenoxy)-1,3,5-triazine, 2-4 parts by mass of an unsaturated stabilizer, and 0.01-0.012 parts by mass of an initiator azobisisobutyronitrile is added dropwise, the addition is terminated after 3 hours, and the reaction is continued by keeping the temperature for 3 hours to obtain the imaging layer resin base material.

[0016] Furthermore, the preparation method of the unsaturated stabilizer tri(allylphenyl)imidazoline is as follows: 53 parts by mass of 4-allylbenzaldehyde, 160 parts by mass of water and 50 parts by mass of ice are placed in a reactor, cooled to 0°C, and immediately injected with 90 parts by mass of 25% ammonia solution under stirring at 600-1000 rpm, naturally heated to 0°C, and then heated to 40°C in a water bath, and stirred at this temperature for 12 hours. After the reaction is completed, it is cooled to room temperature, filtered, washed with water, and dried in air, and then heated to 60°C with 110 parts by mass of DMF and 2.74 parts by mass of 80% sodium ethoxide under nitrogen protection, maintained at this temperature for 10 hours, and then heated until refluxed for 6-8 hours, and then cooled to room temperature, water was added, solids were precipitated, filtered, washed with water, and dried to obtain the unsaturated stabilizer tri(allylphenyl)imidazoline.

[0017] Furthermore, the preparation method of the protective layer resin base material is as follows: 40 parts by mass of xylene are placed in a reaction container, the temperature is raised to 84-86° C. while stirring, and then 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, 2-4 parts by mass of glycidyl acrylate, and 0.01-0.012 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 imaging layer resin base material.

[0018] By adopting the above technical solution, the present invention has the following beneficial effects: The thin offset cold stamping material of the invention comprises a base film layer, a release layer coated on the base film layer, an imaging layer coated on the release layer, an aluminum-plated layer coated on the imaging layer, and a protective adhesive layer coated on the aluminum-plated layer; the imaging layer raw material components comprise: butanone, ethyl acetate, an imaging layer resin base material, and toner; the imaging layer resin base material is obtained by copolymerization of methyl methacrylate, hydroxyethyl methacrylate, unsaturated stabilizer tri(allylphenyl)imidazoline, and 2,4,6-tri(2-allylphenoxy)-1,3,5-triazine; the release layer raw material components comprise: tetraethyl orthosilicate, octaphenylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane, a dimethylsiloxane mixed ring body, n-heptane, and 3,5-di-tert-butyl salicylaldehyde; the protective adhesive layer comprises: methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, xylene, and glycidyl acrylate.

[0019] The base film layer adopts 6U BOPET film, so that the prepared thin offset cold stamping material is thinner than the traditional cold stamping material.

[0020] The release layer material is composed of tetraethyl orthosilicate, octaphenylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane, a dimethylsiloxane mixed ring, n-heptane and 3,5-di-tert-butyl salicylaldehyde; the release layer uses a silicon-based release agent to improve the wear resistance and transparency of the release layer, thereby improving the wear resistance of the thin offset cold stamping material; in addition, the addition of the antioxidant 3,5-di-tert-butyl salicylaldehyde can enhance the anti-aging properties of the release layer material.

[0021] The imaging layer material includes methyl methacrylate, hydroxyethyl methacrylate, an unsaturated stabilizer (tri(allylphenyl)imidazoline) and 2,4,6-tri(2-allylphenoxy)-1,3,5-triazine; these components are copolymerized through unsaturated bonds to form an acrylic copolymer with a hyperbranched structure, thereby enhancing the mechanical properties of the imaging layer material; then, the copolymer is dissolved in butanone and mixed with ethyl acetate and toner; during this process, the unsaturated stabilizer tri(allylphenyl)imidazoline is dispersed on the molecular chain of the acrylic copolymer with a hyperbranched structure, and as a free radical scavenger, it can capture and neutralize free radicals generated by heat, light or oxidation reactions, prevent polymer chain breakage, and decompose peroxides, thereby improving the antioxidant properties of the imaging layer material.

[0022] Subsequently, the coated imaging layer is immersed in an aluminum acetate mixture for ultrasonic immersion treatment; the aluminum acetate mixture penetrates into the cavities of the imaging layer, and the precipitation formed by the hydrolysis of aluminum acetate fills these cavities, making the imaging layer smoother; at the same time, under the action of acetic anhydride in the aluminum acetate mixture, the tri(allylphenyl)imidazoline in the imaging layer is converted into 1,2-diphenyl-1,2-ethylenediamine. The amino group on this compound undergoes a cross-linking reaction with the aldehyde group in the release layer, thereby firmly combining the release layer and the imaging layer.

[0023] Finally, vacuum aluminum is plated on the smooth surface of the imaging layer. During the vacuum aluminum plating process, some aluminum atoms diffuse into the aluminum oxide lattice evenly distributed in the imaging layer, or the oxygen atoms in the aluminum oxide diffuse into the aluminum coating, forming a transition zone. The existence of this transition zone strengthens the interfacial bonding between the two materials, making the aluminum coating more uniform, which not only enhances the adhesion between the imaging layer and the aluminum coating, but also improves the overall glossiness of the thin offset cold stamping material. DETAILED DESCRIPTION

[0024] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with specific implementation methods.

[0025] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without making any creative work shall fall 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.

[0028] The following are some sources of raw materials for the examples and comparative examples: Dimethylsiloxane mixed ring (DMC, the main component is octamethylcyclotetrasiloxane), industrial grade, Momentive High-tech Materials (Nantong) Co., Ltd.

[0029] (Example 1) A preparation process for a thin offset cold foil material, comprising the following preparation steps: (1) Preparation of release coating: 75 parts by weight of dimethylsiloxane mixed ring body was placed in a 50°C reactor, and water was removed for 28 minutes under a nitrogen atmosphere and -0.095 MPa. Then, 15 parts by weight of tetravinyltetramethylcyclotetrasiloxane, 5 parts by weight of octaphenylcyclotetrasiloxane and 150 ppm of catalyst methanol potassium alkali glue were added, and water was continued to be removed for 28 minutes under a nitrogen atmosphere and -0.095 MPa. Then, the temperature was raised to 170°C, and after reacting for 80 minutes, naturally cooled to room temperature, 0.0003 parts by weight of tris(trimethylsilyl) phosphate was added, and after stirring at room temperature for 28 minutes, unreacted monomers were removed under reduced pressure at 200°C nitrogen atmosphere and -0.095 MPa to recover the unreacted monomers. Then, the temperature was lowered to 90°C, 20 ppm of chloroplatinic acid catalyst was added, and the reaction was continued at a constant temperature for 4 minutes. h and then cooled to room temperature, adding 40 parts by mass of polydimethylsiloxane, 5 parts by mass of 3,5-di-tert-butyl salicylaldehyde, and 50 parts by mass of n-heptane to obtain a release layer coating; (2) Preparation of imaging layer coating: 30 parts by weight of butanone was added into a stirring barrel, and stirred evenly at a constant temperature of 25° C. for 5 min. Then, 5 parts by weight of ethyl acetate, 40 parts by weight of imaging layer resin base material, and 1 part by weight of toner were added into the stirring barrel in sequence, and stirred while adding. After the addition was completed, stirring was continued for 23 hours to obtain an imaging coating; (3) Preparation of protective coating: Add 20 parts by weight of xylene into a stirring barrel, stir evenly at a constant temperature of 25° C. for 5 minutes, then add 60 parts by weight of protective layer resin base material into the stirring barrel, stirring while adding, and continue stirring for 30 minutes after the addition is complete to obtain a protective coating; (4) First, a 0.3 μm thick release coating is coated on the base film layer and then dried. Then, a 0.3 μm thick imaging layer is coated on the release coating and then dried. Subsequently, the material is immersed in 100 parts by weight of aluminum acetate mixed solution and heated to 135° C. for ultrasonic immersion for 7 hours. Subsequently, 11 parts by weight of 40% hydrogen bromide aqueous solution is added and ultrasonic immersion is continued for 4 hours. After being taken out, the material is placed in 10 parts by weight of methanol and ultrasonic immersion is continued at room temperature for 24 hours. After being taken out and dried, a 380 angstrom thick aluminum layer is vacuum plated on the immersed imaging layer. Finally, a 0.3 μm protective coating is coated on the aluminum layer and then dried to form a thin offset cold stamping material.

[0030] The base film layer is made of 6U BOPET film.

[0031] The preparation method of the catalyst potassium methoxide gel is as follows: 20 parts by mass of a dimethylsiloxane mixed ring body is placed in a 50° C. reactor, and water is removed for 28 minutes under a nitrogen atmosphere and −0.095 MPa. Then, 0.3 parts by mass of potassium methoxide is quickly added, and water is continued to be removed for 28 minutes under a nitrogen atmosphere and −0.095 MPa. Then, the temperature is raised to 110° C., and the reaction is carried out for 2 hours at an appropriate stirring rate to obtain potassium methoxide gel, which is then filled with nitrogen and stored at a low temperature for later use.

[0032] The preparation method of the imaging layer resin base material is as follows: 40 parts by weight of xylene is placed in a reaction container, the temperature is raised to 84° C. while stirring, and then a mixture of 2.5 parts by weight of methyl methacrylate, 2 parts by weight of hydroxyethyl methacrylate, 2 parts by weight of 2,4,6-tris(2-allylphenoxy)-1,3,5-triazine, 2 parts by weight of an unsaturated stabilizer, and 0.01 parts by weight of an initiator azobisisobutyronitrile is added dropwise, the addition is terminated after 3 hours, and the reaction is continued by keeping the temperature for 3 hours to obtain the imaging layer resin base material.

[0033] The preparation method of the unsaturated stabilizer tri(allylphenyl)imidazoline is as follows: 53 parts by mass of 4-allylbenzaldehyde, 160 parts by mass of water and 50 parts by mass of ice are placed in a reactor, cooled to 0°C, and immediately injected with 90 parts by mass of 25% ammonia solution under stirring at 600 rpm, naturally heated to 0°C, and then heated to 40°C in a water bath, and stirred at this temperature for 12 hours. After the reaction is completed, it is cooled to room temperature, filtered, washed with water, and dried in air, and then heated to 60°C with 110 parts by mass of DMF and 2.74 parts by mass of 80% sodium ethoxide under nitrogen protection, maintained at this temperature for 10 hours, and then heated until refluxed for 6 hours, and then cooled to room temperature, water was added, solids were precipitated, filtered, washed with water, and dried to obtain the unsaturated stabilizer tri(allylphenyl)imidazoline.

[0034] The preparation method of the protective layer resin base material is as follows: 40 parts by weight of xylene is placed in a reaction container, the temperature is raised to 84° C. while stirring, and then a mixture of 2.5 parts by weight of methyl methacrylate, 2 parts by weight of hydroxyethyl methacrylate, 2 parts by weight of butyl acrylate, 2 parts by weight of glycidyl acrylate, and 0.01 parts by weight of initiator azobisisobutyronitrile is added dropwise, the addition is terminated after 3 hours, and the reaction is continued by keeping the temperature for 3 hours to obtain the imaging layer resin base material.

[0035] (Example 2) A preparation process for a thin offset cold foil material, comprising the following preparation steps: (1) Preparation of release coating: 78 parts by weight of dimethylsiloxane mixed ring body was placed in a reactor at 50°C, and water was removed for 30 minutes under a nitrogen atmosphere and -0.095 MPa. Then, 15 parts by weight of tetravinyltetramethylcyclotetrasiloxane, 10 parts by weight of octaphenylcyclotetrasiloxane and 150 ppm of catalyst methanol potassium alkali glue were added, and water was continued to be removed for 30 minutes under a nitrogen atmosphere and -0.095 MPa. Then, the temperature was raised to 170°C, and after reacting for 90 minutes, naturally cooled to room temperature, 0.0003 parts by weight of tris(trimethylsilyl) phosphate was added, and after stirring at room temperature for 29 minutes, unreacted monomers were removed under reduced pressure at 200°C in a nitrogen atmosphere and -0.095 MPa to recover the unreacted monomers. Then, the temperature was lowered to 90°C, 20 ppm of chloroplatinic acid catalyst was added, and the reaction was continued at a constant temperature for 4 minutes. h and then cooled to room temperature, adding 45 parts by mass of polydimethylsiloxane, 10 parts by mass of 3,5-di-tert-butyl salicylaldehyde, and 55 parts by mass of n-heptane to obtain a release layer coating; (2) Preparation of imaging layer coating: 40 parts by weight of butanone was added into a stirring barrel and stirred evenly at a constant temperature of 28° C. for 10 min. Then, 8 parts by weight of ethyl acetate, 50 parts by weight of imaging layer resin base material and 2 parts by weight of toner were added into the stirring barrel in sequence while stirring. After the addition was completed, stirring was continued for 24 hours to obtain an imaging coating; (3) Preparation of protective coating: Add 30 parts by weight of xylene into a stirring barrel, stir evenly at a constant temperature of 28° C. for 8 minutes, then add 70 parts by weight of protective layer resin base material into the stirring barrel, stirring while adding, and continue stirring for 45 minutes after the addition is complete to obtain a protective coating; (4) First, a 0.3 μm thick release coating is coated on the base film layer and then dried. Then, a 0.3 μm thick imaging layer coating is coated on the release coating and then dried. Subsequently, the coating is immersed in 100 parts by weight of aluminum acetate mixed solution and heated to 140°C for ultrasonic immersion for 8 hours. Subsequently, 11.5 parts by weight of 40% hydrogen bromide aqueous solution is added and ultrasonic immersion is continued for 4 hours. After being taken out, the coating is placed in 10 parts by weight of methanol and ultrasonic immersion is continued at room temperature for 24 hours. After being taken out and dried, a 300 angstrom thick aluminum coating is vacuum plated on the immersed imaging layer. Finally, a 0.3 μm thick protective coating is coated on the aluminum coating and then dried to form a thin offset cold stamping material.

[0036] The base film layer is made of 6U BOPET film.

[0037] The preparation method of the catalyst potassium methoxide gel is as follows: 20 parts by mass of a dimethylsiloxane mixed ring body is placed in a 50° C. reactor, and water is removed for 30 minutes under a nitrogen atmosphere and −0.095 MPa. Then, 0.3 parts by mass of potassium methoxide is quickly added, and water is continued to be removed for 30 minutes under a nitrogen atmosphere and −0.095 MPa. Then, the temperature is raised to 110° C., and the reaction is carried out for 2 hours at an appropriate stirring rate to obtain potassium methoxide gel, which is then filled with nitrogen and stored at a low temperature for later use.

[0038] The preparation method of the imaging layer resin base material 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 2,4,6-tris(2-allylphenoxy)-1,3,5-triazine, 3 parts by mass of an unsaturated stabilizer, and 0.011 parts by mass of an initiator azobisisobutyronitrile is added dropwise, the addition is terminated after 3 hours, and the reaction is continued by keeping the temperature for 3 hours to obtain the imaging layer resin base material.

[0039] The preparation method of the unsaturated stabilizer tri(allylphenyl)imidazoline is as follows: 53 parts by mass of 4-allylbenzaldehyde, 160 parts by mass of water and 50 parts by mass of ice are placed in a reactor, cooled to 0°C, and immediately injected with 90 parts by mass of 25% ammonia solution under stirring at 800 rpm, naturally heated to 0°C, and then heated to 40°C in a water bath, and stirred at this temperature for 12 hours. After the reaction is completed, it is cooled to room temperature, filtered, washed with water, and dried in air, and then heated to 60°C with 110 parts by mass of DMF and 2.74 parts by mass of 80% sodium ethoxide under nitrogen protection, maintained at this temperature for 10 hours, and then heated until refluxed for 7 hours, and then cooled to room temperature, water was added, solids were precipitated, filtered, washed with water, and dried to obtain the unsaturated stabilizer tri(allylphenyl)imidazoline.

[0040] The preparation method of the protective layer resin base material 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, 3 parts by mass of glycidyl acrylate, 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 imaging layer resin base material.

[0041] (Example 3) A preparation process for a thin offset cold foil material, comprising the following preparation steps: (1) Preparation of release coating: 80 parts by weight of dimethylsiloxane mixed ring body was placed in a reactor at 50°C, and water was removed for 32 minutes under a nitrogen atmosphere and -0.095 MPa. Subsequently, 15 parts by weight of tetravinyltetramethylcyclotetrasiloxane, 15 parts by weight of octaphenylcyclotetrasiloxane and 150 ppm of catalyst methanol potassium alkali glue were added, and water was continued to be removed for 32 minutes under a nitrogen atmosphere and -0.095 MPa. Subsequently, the temperature was raised to 170°C, and after reacting for 100 minutes, the mixture was naturally cooled to room temperature, and then 0.0003 parts by weight of tris(trimethylsilyl) phosphate was added. After stirring at room temperature for 30 minutes, unreacted monomers were removed under reduced pressure at 200°C in a nitrogen atmosphere and -0.095 MPa to recover the unreacted monomers. Subsequently, the temperature was lowered to 90°C, 20 ppm of chloroplatinic acid catalyst was added, and the reaction was continued at a constant temperature for 4 minutes. h and then cooled to room temperature, adding 50 parts by mass of polydimethylsiloxane, 15 parts by mass of 3,5-di-tert-butyl salicylaldehyde, and 60 parts by mass of n-heptane to obtain a release layer coating; (2) Preparation of imaging layer coating: 50 parts by weight of butanone was added into a stirring barrel, and stirred evenly at a constant temperature of 30°C for 15 minutes. Then, 10 parts by weight of ethyl acetate, 60 parts by weight of imaging layer resin base material, and 3 parts by weight of toner were added into the stirring barrel in sequence, and stirred while adding. After the addition was completed, stirring was continued for 25 hours to obtain an imaging coating; (3) Preparation of protective coating: Add 40 parts by weight of xylene into a stirring barrel, stir evenly at a constant temperature of 30° C. for 10 min, then add 80 parts by weight of protective layer resin base material into the stirring barrel, stirring while adding, and continue stirring for 60 min after adding, to obtain a protective coating; (4) First, a 0.3 μm thick release coating is coated on the base film layer and then dried. Then, a 0.3 μm thick imaging layer coating is coated on the release coating and then dried. Subsequently, the coating is immersed in 100 parts by weight of aluminum acetate mixed solution and heated to 145°C for ultrasonic immersion for 9 hours. Subsequently, 12 parts by weight of 40% hydrogen bromide aqueous solution is added and ultrasonic immersion is continued for 4 hours. After being taken out, the coating is placed in 10 parts by weight of methanol and ultrasonic immersion is continued at room temperature for 24 hours. After being taken out and dried, a 320 angstrom thick aluminum coating is vacuum plated on the immersed imaging layer. Finally, a 0.3 μm thick protective coating is coated on the aluminum coating and then dried to form a thin offset cold stamping material.

[0042] The base film layer is made of 6U BOPET film.

[0043] The preparation method of the catalyst potassium methoxide gel is as follows: 20 parts by mass of a dimethylsiloxane mixed ring body is placed in a 50° C. reactor, and water is removed for 32 minutes under a nitrogen atmosphere and −0.095 MPa. Subsequently, 0.3 parts by mass of potassium methoxide is quickly added, and water is continued to be removed for 32 minutes under a nitrogen atmosphere and −0.095 MPa. Subsequently, the temperature is raised to 110° C., and the reaction is carried out for 2 hours at an appropriate stirring rate to obtain potassium methoxide gel, which is then filled with nitrogen and stored at a low temperature for later use.

[0044] The preparation method of the imaging layer resin base material 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 2,4,6-tris(2-allylphenoxy)-1,3,5-triazine, 4 parts by mass of an unsaturated stabilizer, and 0.012 parts by mass of an initiator azobisisobutyronitrile is added dropwise, the addition is terminated after 3 hours, and the reaction is continued by keeping the temperature for 3 hours to obtain the imaging layer resin base material.

[0045] The preparation method of the unsaturated stabilizer tri(allylphenyl)imidazoline is as follows: 53 parts by mass of 4-allylbenzaldehyde, 160 parts by mass of water and 50 parts by mass of ice are placed in a reactor, cooled to 0°C, and immediately injected with 90 parts by mass of 25% ammonia solution under stirring at 1000rpm, naturally heated to 0°C, and then heated to 40°C in a water bath, and stirred at this temperature for 12h. After the reaction is completed, it is cooled to room temperature, filtered, washed with water, and dried in air, and then heated to 60°C with 110 parts by mass of DMF and 2.74 parts by mass of 80% sodium ethoxide under nitrogen protection, maintained at this temperature for 10h, and then heated until refluxed for 8h, and then cooled to room temperature, water is added, solid is precipitated, filtered, washed with water, and dried to obtain the unsaturated stabilizer tri(allylphenyl)imidazoline.

[0046] The preparation method of the protective layer resin base material 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, 4 parts by mass of glycidyl acrylate, 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 imaging layer resin base material.

[0047] Comparative Example 1 The only difference between Comparative Example 1 and Example 2 is that the raw material components of the release layer coating include, by weight: 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; the remaining steps and components are the same as those in Example 2.

[0048] Comparative Example 2 The only difference between Comparative Example 2 and Example 2 is that the raw material components of the release layer include: tetraethyl orthosilicate, octaphenylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane, dimethylsiloxane mixed ring body, n-heptane, tri(trimethylsilyl) phosphate, polydimethylsiloxane, and antioxidant 1010; the remaining steps and components are the same as Example 2.

[0049] Comparative Example 3 The difference between Comparative Example 3 and Example 2 is that the raw material components of the imaging layer resin base material include 2.5 parts by weight of methyl methacrylate, 2 to 3 parts by weight of hydroxyethyl methacrylate, 2 parts by weight of butyl methacrylate, 2 to 4 parts by weight of unsaturated stabilizer, 0.01 to 0.012 parts by weight of initiator, and 40 parts by weight of xylene; the remaining steps and components are the same as those in Example 2.

[0050] Comparative Example 4 The difference between Comparative Example 4 and Example 2 is that the raw material components of the imaging layer resin base material include 2.5 parts by weight of methyl methacrylate, 2 to 3 parts by weight of hydroxyethyl methacrylate, 2 parts by weight of 2,4,6-tris(2-allylphenoxy)-1,3,5-triazine, 2 to 4 parts by weight of antioxidant 1010, 0.01 to 0.012 parts by weight of initiator, and 40 parts by weight of xylene; the remaining steps and components are the same as those in Example 2.

[0051] Comparative Example 5 The difference between Comparative Example 5 and Example 2 is only step (4). The specific steps of step (4) are as follows: first, a 0.3 μm thick release coating is coated on the base film layer and then dried, then a 0.3 μm thick imaging layer is coated on the release coating and then dried, then a 240 angstrom thick aluminum coating is vacuum-coated on the imaging layer, and finally a 0.3 μm thick protective coating is coated on the aluminum layer and then dried to form a thin offset cold stamping material; the remaining steps and components are the same as those in Example 2.

[0052] Effect example: Tensile performance test: The thin offset cold stamping materials prepared in the examples and comparative examples were tested for tensile properties according to GB / T228.1.

[0053] Glossiness: The glossiness of the thin offset cold foil materials prepared in the examples and comparative examples was tested at an incident angle of 60°.

[0054] Abrasion resistance: The thin offset cold stamping materials prepared in the examples and comparative examples were tested using a LXD-A digital display Shore hardness tester.

[0055] Peeling test: The thin offset cold foil materials prepared in the examples and comparative examples were subjected to peeling test. The peeling test was conducted by using an adhesive tape to stick to the protective layer and then tearing it to test the separation of the thin offset cold foil materials.

[0056] Table 1 Shore Hardness Tensile strength (MPa) Glossiness (GU) Peel test Example 1 92.6 14.97 76 Separate the base film from the release layer Example 2 94.3 15.41 82 Separate the base film from the release layer Example 3 90.3 15.19 78 Separate the base film from the release layer Comparative Example 1 60.2 14.62 68 Release layer and imaging layer are separated Comparative Example 2 90.4 14.86 70 Release layer and imaging layer are separated Comparative Example 3 90.6 11.36 53 Aluminum coating and imaging layer are separated Comparative Example 4 92.8 13.76 72 Release layer and imaging layer are separated Comparative Example 5 92.5 14.58 66 Aluminum coating and imaging layer are separated Table 1 below shows the performance test results of the thin offset cold foil materials prepared in the examples and comparative examples: Referring to Table 1, compared with the embodiment and the comparative example, the silk screen cold stamping gold foil prepared in the embodiment has better wear resistance, mechanical properties, higher gloss, and better adhesion between the release layer, imaging layer, aluminum plating layer, and protective layer; compared with Example 2, the release layer is prepared by using tetraethyl orthosilicate, octaphenylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane, dimethylsiloxane mixed ring body, n-heptane, 3,5-di-tert-butyl salicylaldehyde, tris (trimethylsilyl) phosphate, and polydimethylsiloxane. The wear resistance, mechanical properties, and gloss of the prepared silk screen cold stamping gold foil are better, and the adhesion between the release layer, imaging layer, aluminum plating layer, and protective layer is better; Compared with Example 2, Examples 3-4 use methyl methacrylate, hydroxyethyl methacrylate, 2,4,6-tris (2-allylphenoxy) -1,3,5-triazine, unsaturated stabilizer, initiator, and xylene to obtain an imaging layer resin base material, and the obtained silk-screen cold stamping gold foil has better mechanical properties and higher gloss, and the adhesion between the release layer, the imaging layer, the aluminum plating layer, and the protective layer is better; Compared with Example 2, the imaging layer is ultrasonically immersed in an aluminum acetate mixed solution and a hydrogen bromide aqueous solution in sequence before vacuum aluminum plating, and the obtained silk-screen cold stamping gold foil has better mechanical properties and higher gloss, and the adhesion between the release layer, the imaging layer, the aluminum plating layer, and the protective layer is better.

[0057] 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 thin offset cold foil material, characterized in that: It comprises a base film layer, a release layer coated on the base film layer, an imaging layer coated on the release layer, an aluminum coating layer vacuum-deposited on the imaging layer, and a protective adhesive layer coated on the aluminum coating layer; the base film layer adopts a 6U BOPET film.

2. The thin offset cold stamping material according to claim 1, characterized in that: The release layer raw material components include: tetraethyl orthosilicate, octaphenylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane, dimethylsiloxane mixed ring body, n-heptane, 3,5-di-tert-butyl salicylaldehyde, tris(trimethylsilyl)phosphate, and polydimethylsiloxane.

3. The thin offset cold stamping material according to claim 1, characterized in that: The imaging layer comprises, by weight, 30 to 50 parts of butanone, 5 to 10 parts of ethyl acetate, 40 to 60 parts of an imaging layer resin base material, and 1 to 3 parts of toner; the imaging layer resin base comprises, by weight, 2.5 parts of methyl methacrylate, 2 to 3 parts of hydroxyethyl methacrylate, 2 parts of 2,4,6-tris(2-allylphenoxy)-1,3,5-triazine, 2 to 4 parts of an unsaturated stabilizer, 0.01 to 0.012 parts of an initiator, and 40 parts of xylene.

4. The thin offset cold stamping material according to claim 1, characterized in that: The raw material components of the protective rubber layer include, by weight: 60-80 parts by weight of a protective layer resin base material and 20-40 parts by weight of xylene; the raw material components of the protective layer resin base material include, by weight: 2.5 parts by weight of methyl methacrylate, 2-3 parts by weight of hydroxyethyl methacrylate, 2 parts by weight of butyl acrylate, 2-4 parts by weight of glycidyl acrylate, 0.01-0.012 parts by weight of an initiator and 40 parts by weight of xylene.

5. The thin offset cold stamping material according to claim 1, characterized in that: The imaging layer is ultrasonically immersed in an aluminum acetate mixed solution and a hydrogen bromide aqueous solution in sequence before vacuum aluminum plating; wherein the aluminum acetate mixed solution comprises, by weight, 50 parts by weight of ethanol, 50 parts by weight of acetic anhydride, 2-4 parts by weight of aluminum acetate, and 1.6-1.7 parts by weight of sodium ethoxide.

6. A process for preparing a thin offset cold stamping material according to any one of claims 1 to 5, characterized in that: The method comprises the following preparation steps: (1) preparing a release layer coating; (2) Preparation of imaging layer coating: Add butanone into a stirring bucket according to the formula ratio, stir evenly at a constant temperature of 25-30°C for 5-15 minutes, then add ethyl acetate, imaging layer resin base material, and color powder into the stirring bucket in order according to the proportion, stirring while adding, and continue stirring for 23-25 ​​hours after adding, to obtain the imaging coating; (3) Preparation of protective coating: Add xylene into a stirring barrel according to the formula ratio, stir evenly at a constant temperature of 25-30°C for 5-10 minutes, then add the protective layer resin base material into the stirring barrel according to the proportion, stirring while adding, and continue stirring for 30-60 minutes after adding to obtain the protective coating; (4) First, a release coating is applied on the base film layer and then dried. Then, an imaging layer is applied on the release coating and then dried. Subsequently, the layer is immersed in 100 parts by weight of an aluminum acetate mixture and heated to 135-145° C. for ultrasonic immersion for 7-9 hours. Subsequently, 11-12 parts by weight of a 40% aqueous hydrogen bromide solution is added and ultrasonic immersion is continued for 4 hours. After being taken out, the layer is placed in 10 parts by weight of methanol and ultrasonic immersion is continued at room temperature for 24 hours. After being taken out and dried, vacuum aluminum is plated on the immersed imaging layer. Finally, a protective coating is applied on the aluminum-plated layer and then dried to form a thin offset cold stamping material.

7. The process for preparing thin offset cold stamping material according to claim 6, characterized in that: The preparation method of the release layer coating is as follows: 75-80 parts by weight of a dimethylsiloxane mixed ring body is placed in a 50° C. reactor, dehydrated for 28-32 minutes under a nitrogen atmosphere and −0.095 MPa, then 15 parts by weight of tetravinyltetramethylcyclotetrasiloxane, 5-15 parts by weight of octaphenylcyclotetrasiloxane and 150 ppm of a catalyst, potassium alkali methanol glue, and dehydrated for 28-32 minutes under a nitrogen atmosphere and −0.095 MPa, then heated to 170° C., reacted for 80-100 minutes, naturally cooled to room temperature, added with 0.0003 parts by weight of tris(trimethylsilyl)phosphate, stirred at room temperature for 28-30 minutes, decompressed and dehydrated to recover unreacted monomers under a 200° C. nitrogen atmosphere and −0.095 MPa, then cooled to 90° C., added with 20 ppm of chloroplatinic acid catalyst, and reacted at a constant temperature for 4 minutes. h and then cooled to room temperature, 40-50 parts by weight of polydimethylsiloxane, 5-15 parts by weight of 3,5-di-tert-butyl salicylaldehyde and 50-60 parts by weight of n-heptane were added to obtain a release layer coating.

8. The process for preparing thin offset cold stamping material according to claim 6, characterized in that: The preparation method of the imaging layer resin base material is as follows: 40 parts by weight of xylene is placed in a reaction container, the temperature is raised to 84-86° C. while stirring, and then a mixture of 2.5 parts by weight of methyl methacrylate, 2-3 parts by weight of hydroxyethyl methacrylate, 2 parts by weight of 2,4,6-tris(2-allylphenoxy)-1,3,5-triazine, 2-4 parts by weight of an unsaturated stabilizer, and 0.01-0.012 parts by weight of an initiator azobisisobutyronitrile is added dropwise, the addition is terminated after 3 hours, and the reaction is continued by keeping the temperature for 3 hours to obtain the imaging layer resin base material.

9. The process for preparing thin offset cold stamping material according to claim 8, characterized in that: The preparation method of the unsaturated stabilizer tri(allylphenyl)imidazoline is as follows: 53 parts by mass of 4-allylbenzaldehyde, 160 parts by mass of water and 50 parts by mass of ice are placed in a reactor, cooled to 0°C, and immediately injected with 90 parts by mass of 25% ammonia solution under stirring at 600-1000 rpm, naturally heated to 0°C, and then heated to 40°C in a water bath, and stirred at this temperature for 12 hours. After the reaction is completed, it is cooled to room temperature, filtered, washed with water, and dried in air, and then heated to 60°C with 110 parts by mass of DMF and 2.74 parts by mass of 80% sodium ethoxide under nitrogen protection, maintained at this temperature for 10 hours, and then heated until refluxed for 6-8 hours, and then cooled to room temperature, water is added, solids are precipitated, filtered, washed with water, and dried to obtain the unsaturated stabilizer tri(allylphenyl)imidazoline.

10. The process for preparing thin offset cold stamping material according to claim 6, characterized in that: The preparation method of the protective layer resin base material is as follows: 40 parts by weight of xylene is placed in a reaction container, and the temperature is raised to 84-86° C. while stirring, and then a mixture of 2.5 parts by weight of methyl methacrylate, 2-3 parts by weight of hydroxyethyl methacrylate, 2 parts by weight of butyl acrylate, 2-4 parts by weight of glycidyl acrylate, and 0.01-0.012 parts by weight of initiator azobisisobutyronitrile is added dropwise, and the addition is terminated after 3 hours, and the reaction is continued by keeping the temperature for 3 hours to obtain the imaging layer resin base material.