CN112521821B - Protective layer coating for cold-stamping film and preparation method and use method thereof - Google Patents
Protective layer coating for cold-stamping film and preparation method and use method thereof Download PDFInfo
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Abstract
The invention provides a protective layer coating for a cold-stamping film, and a preparation method and a use method thereof. The protective layer coating comprises the following components in parts by weight: 10-20 parts of acrylic resin liquid, 6-12 parts of polyester type polyurethane resin, 3-5 parts of carboxyl ternary vinyl chloride-vinyl acetate resin, 3-5 parts of hydroxyl ternary vinyl chloride-vinyl acetate resin, 2-5 parts of fumed silica, 60-80 parts of ethyl acetate, 10-20 parts of methyl acetate, 6-18 parts of butanone and 0.1-0.3 part of dispersing agent. The cold-stamping film prepared by using the protective layer coating for the cold-stamping film has the advantages of fine and uniform film surface, no back adhesion, excellent high-temperature and high-humidity resistance and high stability; the adhesive force to the aluminized layer and the UV cold-ironing glue layer is strong, the fastness is good, the trimming is neat, the details are clear, and the cold-ironing glue layer is suitable for cold-ironing requirements of pretreated or untreated non-shrinkable paper; the cold-stamping product has unique metallic luster and the effects of large area and small fineness, and the production process and the product are both low in VOCs.
Description
Technical Field
The invention belongs to the technical field of coatings, relates to a protective layer coating and a preparation method and a using method thereof, and particularly relates to a protective layer coating for a cold stamping film and a preparation method and a using method thereof.
Background
With the increasing progress of science and technology and the continuous pursuit of people on environment-friendly products and even environment-friendly production, the cold stamping technology is more and more emphasized and developed due to the unique advantages of the cold stamping technology. The breakthrough of the cold stamping technology benefits from high and new technologies in European and American industries, the existing cold stamping technology is different from the traditional hot stamping technology of transferring the electrochemical aluminum foil by hot pressing, the cold stamping technology uses the new cold pressing technology to transfer the electrochemical aluminum foil, the cold stamping technology is widely used in various printing industries nowadays, and the hot stamped product also has the unique metallic luster which is not inferior to the traditional hot stamping and the effect of considering large area and small fineness. The cold gold stamping technology also avoids the pollution to the environment in the process of manufacturing the metal printing plate and can greatly save energy in the printing process.
The cold stamping film consists of a base material, a release layer, a coloring layer, an aluminum coating and a protective layer. During hot stamping, unlike the hot stamping process in which a layer is coated on the back of the film, the cold stamping technology is to directly coat a special UV cold stamping adhesive on the position of a printed matter to be decorated during printing. When the cold stamping film is contacted with the printed matter, the alumite is transferred and adhered to the surface of the printed matter, which is coated with the adhesive and needs to be stamped, due to the solidification of the adhesive. In the gold stamping process, the protective layer plays a role in enhancing the binding force of the cold stamping film and the UV cold stamping glue and increasing the adhesion fastness of the gold stamping patterns; on the other hand, the cold stamping film has lasting rolling storage stability due to the coating of the protective layer.
CN107325760A discloses an alcohol water-soluble flexo printing cold stamping gum and a preparation method thereof, wherein the gum comprises the following components in parts by weight: 5-15 parts of polyvinylpyrrolidone, 0-30 parts of polar polyacrylic acid resin, 0-10 parts of modified alcohol-soluble polyurethane resin, 0-10 parts of polyvinyl alcohol, 25-40 parts of alcohol solvent, 10-30 parts of distilled water, 0-0.05 part of defoaming agent and 5-10 parts of silicon dioxide. The alcohol water-soluble flexographic printing cold-stamping back adhesive has excellent trimming, excellent bonding fastness with UV cold-stamping adhesive and excellent adhesive force with an aluminum coating; and is economical, environmentally friendly, has ultra-low VOC residue and release, and does not have pungent odor. However, the environment-friendly water-based back adhesive has limited applicability in the current downstream industrial computer, has the potential risks of back adhesion and no high temperature and humidity resistance, and has extremely low computer efficiency in downstream enterprises.
CN111138922A discloses an offset cold wave coating giving consideration to both large field and thin lines and a preparation method thereof, wherein the coating comprises a release coating, a color layer coating and a protective adhesive coating; the release comprises the following components: 1-10% of oleophylic fumed silica, 0.1-5% of stripping auxiliary agent, 1-20% of acrylic resin, 5-30% of cellulose resin and 50-89% of solvent; the color layer coating comprises the following components: 10-30% of acrylic resin, 0.1-2% of polyurethane resin and 68-88% of solvent; the protective adhesive coating comprises the following components: 10-20% of acrylic resin, 1-20% of tackifying resin, 1-10% of oleophylic fumed silica and 50-88% of solvent. According to the invention, by comprehensively regulating and controlling the release layer, the color layer and the protective glue layer coating, the developed product can realize both large-field and fine line hot stamping, and is loose in stripping, high in hot stamping speed, low in cost and suitable for large-scale popularization and use. However, a solvent-based protective adhesive is used, which takes esters, ketones, toluene, dimethyl carbonate, methylcyclohexane and the like as solvents, and contains toluene, butanone and other solvents, which have certain influence on the health of operators and are not environment-friendly; meanwhile, acrylic resin such as Bolim MB-12, tesmann B-811 and the like is used as imported resin as a main functional component, so that the cost is high.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a protective layer coating for a cold-stamping film and a preparation method and a using method thereof, the protective layer coating for the cold-stamping film can obtain an environment-friendly cold-stamping film, has strong adhesive force to an aluminum-plated layer and a UV cold-stamping adhesive layer, good fastness, neat edge cutting, clear details and excellent ironing property, and is suitable for the cold-stamping requirements of pretreated or untreated non-shrinkable paper; the surface of the film layer is fine, uniform and non-sticky, and has excellent high-temperature and high-humidity resistance and high stability; the cold-ironing product has unique metallic luster and the effects of large area and small fineness, and the production process and the product are both low in VOCs.
One of the purposes of the invention is to provide a protective layer coating for a cold stamping film, and in order to achieve the purpose, the invention adopts the following technical scheme:
the protective layer coating for the cold stamping film comprises the following raw materials in parts by weight:
the protective layer coating for the cold stamping film mainly uses a self-made acrylic resin, a polyester polyurethane resin and two kinds of vinyl chloride-vinyl acetate resins, and is matched with fumed silica, so that good cold stamping coating and upper stamping effects are provided. Meanwhile, the dispersing agent is added besides the matrix resin and the filler, so that the high efficiency of the production process and the effectiveness of the coating use are improved; the invention uses ethyl acetate and methyl acetate as main solvents, does not contain non-environment-friendly solvents such as toluene and the like, and also meets the environment-friendly requirement of the thermoprinting material on low VOCs.
The protective layer coating for the cold-stamping film can obtain an environment-friendly cold-stamping film, has strong adhesive force to an aluminum-plated layer and a UV cold-stamping adhesive layer, good fastness, neat trimming, clear details and excellent ironing property, and is suitable for cold-stamping requirements of pretreated or untreated non-shrinkable paper; the surface of the film layer is fine, uniform and non-sticky, and has excellent high-temperature and high-humidity resistance and high stability; the cold-ironing product has unique metallic luster and the effects of large area and small fineness, and the production process and the product are both low in VOCs.
The protective layer coating for the cold stamping film has high independent research and development content, simple and convenient manufacture and high added value; by using the protective layer coating for the cold-stamping film, the coating film surface is uniform and fine, the stability is good, and the coating has good matching property with the coating of the existing part of the coloring layer; meanwhile, the hot stamping property is excellent, the details are clear, and the cold stamping method is suitable for the cold stamping requirements of the pretreated or untreated non-shrink paper.
Specifically, the protective layer coating for the cold stamping film comprises the following components in parts by weight:
10-20 parts of acrylic resin liquid, for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts of the acrylic resin liquid.
6-12 parts of polyester polyurethane resin, for example, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts or 12 parts by weight of polyester polyurethane resin.
3-5 parts of carboxyl ternary vinyl chloride-vinyl acetate, for example, 3 parts, 3.1 parts, 3.2 parts, 3.3 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.7 parts, 3.8 parts, 3.9 parts, 4 parts, 4.1 parts, 4.2 parts, 4.3 parts, 4.4 parts, 4.5 parts, 4.6 parts, 4.7 parts, 4.8 parts, 4.9 parts or 5 parts of carboxyl ternary vinyl chloride-vinyl acetate, and the like.
3-5 parts of hydroxyl ternary vinyl chloride-vinyl acetate copolymer, for example, 3 parts, 3.1 parts, 3.2 parts, 3.3 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.7 parts, 3.8 parts, 3.9 parts, 4 parts, 4.1 parts, 4.2 parts, 4.3 parts, 4.4 parts, 4.5 parts, 4.6 parts, 4.7 parts, 4.8 parts, 4.9 parts or 5 parts of hydroxyl ternary vinyl chloride-vinyl acetate copolymer.
2-5 parts of fumed silica, for example, 2 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.7 parts, 2.8 parts, 2.9 parts, 3 parts, 3.1 parts, 3.2 parts, 3.3 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.7 parts, 3.8 parts, 3.9 parts, 4 parts, 4.1 parts, 4.2 parts, 4.3 parts, 4.4 parts, 4.5 parts, 4.6 parts, 4.7 parts, 4.8 parts, 4.9 parts or 5 parts by weight of fumed silica, etc.
60-80 parts of ethyl acetate, for example, 60 parts, 65 parts, 70 parts, 75 parts or 80 parts of ethyl acetate.
10-20 parts of methyl acetate, for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts of methyl acetate.
6-18 parts of butanone, for example, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts or 18 parts by weight of butanone is used.
0.1 to 0.3 part of dispersant, for example, 0.1 part, 0.2 part or 0.3 part of dispersant by weight.
The acrylic resin liquid is prepared from the following components in parts by weight:
30-40 parts of n-butyl methacrylate, for example, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, etc. of n-butyl methacrylate.
5-10 parts of methacrylic acid, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc. of methacrylic acid.
4-8 parts of hydroxyethyl acrylate, for example, 4 parts, 5 parts, 6 parts, 7 parts or 8 parts of hydroxyethyl acrylate.
0.1 to 0.5 part of dibenzoyl peroxide, for example, 0.1 part, 0.2 part, 0.3 part, 0.4 part or 0.5 part of dibenzoyl peroxide.
40-60 parts of ethyl acetate, for example, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts or 60 parts of ethyl acetate.
The acrylic resin provided by the invention is prepared by taking a small amount of hydroxyethyl acrylate as an internal crosslinking monomer and taking n-butyl methacrylate and methacrylic acid as soft and hard monomers, has a weak crosslinking network structure, and has a lower glass transition temperature and a lower viscosity. The acrylic resin has excellent leveling property and film-forming property, has good adhesive force to an aluminum coating layer and UV cold-ironing glue, has good compatibility to meteorological white carbon black, is stable to store and is convenient to machine. The acrylic resin has lower glass transition temperature and low viscosity which are suitable for cold wave. In addition, the acrylic resin has a certain crosslinking structure, and provides a certain flexibility for the final protective layer.
The polyester polyurethane resin is a polyurethane hot melt adhesive, the special polyester polyurethane has rich ester groups, carbamate and other various polar groups and polymethylene and other non-polar groups, has good adhesion to an aluminum coating, and has high adhesion to a UV cold-hot glue layer mainly made of multifunctional polyester acrylate (PEA), polyurethane acrylate (PUA) and the like; meanwhile, the molecules can form hydrogen bonds, and the molecules have a certain degree of hydrogen bond effect with independently developed acrylic resin, have proper cohesive force and are beneficial to slitting of cold-stamping film printing. The polyester type polyurethane resin is polyester type polyurethane resin of Luobo moist TPU5702-TPU5715 series and/or Desmodium 530, and preferably, the glass transition temperature of the polyester type polyurethane resin is-29-55 ℃.
The carboxyl content of the carboxyl ternary vinyl chloride-acetate copolymer is 2-4%, such as 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9% or 4%, and the like, and the carboxyl ternary vinyl chloride-acetate copolymer is selected to have excellent adhesion to metal, so that the adhesion of the protective adhesive layer to the aluminum plating layer is provided.
The hydroxyl content of the hydroxyl ternary vinyl chloride-vinyl acetate copolymer resin is 1.8-2.2%, for example, the hydroxyl content is 1.8%, 1.9%, 2%, 2.1% or 2.2%, and the like, and the hydroxyl ternary vinyl chloride-vinyl acetate copolymer resin has certain adhesive force, and has stronger intermolecular force generation with acrylic resin, so that the cohesive force of the coating is improved.
The specific surface area of the fumed silica is 100-150m 2 Per g, e.g. fumed silica, having a specific surface area of 100m 2 /g、110m 2 /g、120m 2 /g、130m 2 /g、140m 2 G or 150m 2 A particle diameter of 10 to 25nm, for example, a particle diameter of 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, 21nm, 22nm, 23nm, 24nm or 25 nm. The fumed silica is a high-tech superfine inorganic filler, the particles of the fumed silica are extremely small, and a three-dimensional chain structure can be formed, and in the optimal proportion, the tension caused by coating on two sides of an aluminum coating layer can be balanced; on the other hand, in the preferable proportion, the inorganic filler does not influence the adhesive force of the main resin to the aluminum coating and the cold-ironing glue, and meanwhile, due to the microstructure and the thickening property, the coating can be provided with good stability and leveling property.
The dispersant is any one or a mixture of at least two of polycarboxylic acid polymer dispersant, phosphate type high molecular polymer dispersant and acrylate dispersant.
The second purpose of the invention is to provide a preparation method of the protective layer coating for the cold stamping film, which comprises the following steps:
1) Preparing acrylic resin liquid;
2) Preparing coating mother liquor: weighing 10-20 parts by weight of acrylic resin liquid prepared in the step 1), 6-12 parts by weight of polyester type polyurethane resin, 3-5 parts by weight of carboxyl ternary vinyl chloride-acetate copolymer resin, 3-5 parts by weight of hydroxyl ternary vinyl chloride-acetate copolymer resin, 2-5 parts by weight of fumed silica, 0.1-0.3 part by weight of dispersant, 25-40 parts by weight of ethyl acetate, 2-5 parts by weight of methyl acetate and 5-10 parts by weight of butanone, stirring uniformly and wetting, continuing stirring, and standing to obtain a coating mother liquid;
3) Preparing a protective layer coating for the cold stamping film: and 2) uniformly stirring and wetting the coating mother liquor obtained in the step 2) and the rest of ethyl acetate, methyl acetate and butanone, continuing stirring, and standing to obtain the protective layer coating for the cold-stamping film.
In the step 1), the preparation method of the acrylic resin liquid comprises the following steps:
dividing n-butyl methacrylate, methacrylic acid and hydroxyethyl acrylate into two parts of a base material and a dropwise addition material with the mass ratio of (1:1) - (1:2), dividing dibenzoyl peroxide into three parts of a base material, a dropwise addition material and a supplemented material with the mass ratio of (1;
a) Adding n-butyl methacrylate, methacrylic acid, hydroxyethyl acrylate, dibenzoyl peroxide and ethyl acetate in the bottom material part into a reaction kettle, stirring and heating up, uniformly stirring until reflux begins to time, then heating up to the reaction temperature of 75-90 ℃, stirring and preserving heat for 1-1.5h;
b) After the heat preservation is finished, injecting the n-butyl methacrylate, the methacrylic acid, the hydroxyethyl acrylate, the dibenzoyl peroxide and the ethyl acetate of the dropwise adding material part into a titration tank to start dropwise adding, keeping the reaction temperature under stirring, and finishing dropwise adding within 2.5-4 h;
c) After the dropwise addition, adding the dibenzoyl peroxide and the ethyl acetate of the supplementary material part, finishing adding Zhong Yunsu, preserving the heat for 1-2h, and reacting to obtain the acrylic resin liquid.
The invention also provides a use method of the protective layer paint for the cold stamping film, which comprises the steps of coating the protective layer paint for the cold stamping film on an electrochemical aluminum foil, drying and rolling.
The using method of the protective layer coating for the cold-stamping film is basically consistent with the traditional electrochemical aluminum protective adhesive process, and the protective layer coating for the cold-stamping film is directly coated on the electrochemical aluminum foil which is sequentially coated with the release layer, the coloring layer and the aluminum coating layer on the base film. The protective layer coating for the cold-stamping film is used, and the coated film surface is uniform, fine and white; meanwhile, the coating amount can be regulated and controlled to perfectly adapt to the existing solvent type coloring layer, the adaptability with cold-ironing glue is good, the ironing property is excellent, the details are clear, the fastness is excellent, and the coating is suitable for the cold-ironing requirement of the pretreated or untreated non-shrinkage paper.
The coating dry weight of the protective layer coating for the cold stamping film is 0.3-0.4g/m 2 For example, a coating dry weight of 0.3g/m 2 、0.31g/m 2 、0.32g/m 2 、0.33g/m 2 、0.34g/m 2 、0.35g/m 2 、0.36g/m 2 、0.37g/m 2 、0.38g/m 2 、0.39g/m 2 Or 0.4g/m 2 Etc.; the drying temperature is 100-140 deg.C, such as 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C or 140 deg.C.
Compared with the prior art, the invention has the following beneficial effects:
the protective layer coating for the cold-stamping film can obtain the environment-friendly cold-stamping film, the surface of the film layer is fine, uniform and does not adhere, the high-temperature and high-humidity resistance is excellent, and the stability is high; the cold-ironing product has unique metallic luster and the effects of large area and small fineness, and the production process and the product are both low in VOCs.
The protective layer coating for the cold stamping film has high independent research and development content, simple and convenient manufacture and high added value; the protective layer coating for the cold-stamping film is uniform and fine in coating film surface, good in stability and good in matching with the existing coating of part of the coloring layer; meanwhile, the hot stamping property is excellent, the details are clear, and the cold stamping method is suitable for the cold stamping requirements of the pretreated or untreated non-shrink paper.
Drawings
FIG. 1 is a schematic structural view of a cold stamping film;
the reference numbers are as follows:
1-a substrate layer; 2-a release layer; 3-a coloured layer; 4-plating an aluminum layer; 5-protective layer.
Detailed Description
The technical solution of the present invention is further described by the following specific embodiments with reference to fig. 1.
Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.
As shown in the attached drawing 1, the cold stamping film comprises a protective layer 5, an aluminum-plated layer 4, a coloring layer 3, a release layer 2 and a substrate layer 1 which are sequentially arranged from top to bottom. The protective layer 5 plays a role in enhancing the binding force of the cold stamping film and the UV cold stamping glue and increasing the adhesion fastness of the hot stamping patterns; the cold-stamping film has lasting rolling storage stability due to the coating of the protective layer 5, and the environment-friendly cold-stamping film can be obtained by using the protective layer coating for the cold-stamping film, the surface of the film layer is fine and uniform without back adhesion, and the cold-stamping film has excellent high-temperature and high-humidity resistance and high stability; the cold-ironing product has unique metallic luster and the effects of large area and small fineness, and the production process and the product are both low in VOCs.
Example 1
The protective layer coating for the cold-stamping film comprises the following raw materials in parts by weight:
wherein the polyester type polyurethane resin is Lu Borun polyester type polyurethane resin TPU5713, the carboxyl content of carboxyl ternary vinyl chloride-acetate copolymer is 2%, the hydroxyl content of hydroxyl ternary vinyl chloride-acetate copolymer is 2.2%, and the specific surface area of fumed silica is 100m 2 The particle size is 12nm, and the dispersant is acrylate dispersant.
The preparation method of the protective layer coating for the cold stamping film comprises the following steps:
1) Preparing acrylic resin liquid;
2) Preparing coating mother liquor: weighing 16 parts of acrylic resin liquid prepared in the step 1), 8 parts of polyester type polyurethane resin, 4.5 parts of carboxyl ternary vinyl chloride-acetate copolymer resin, 4.5 parts of hydroxyl ternary vinyl chloride-acetate copolymer resin, 5 parts of fumed silica, 0.1 part of dispersing agent, 40 parts of ethyl acetate, 4 parts of methyl acetate and 10 parts of butanone, stirring uniformly and wetting, continuing stirring for 3 hours, and standing for 2 hours to obtain coating mother liquid;
3) Preparing a protective layer coating for the cold stamping film: and 2) stirring the coating mother liquor obtained in the step 2) and the rest of ethyl acetate, methyl acetate and butanone uniformly, wetting, continuing stirring for 1h, and standing for 1h to obtain the protective layer coating for the cold-stamping film.
The acrylic resin liquid is prepared from the following components in parts by weight:
the preparation method of the acrylic resin liquid of this example is as follows:
dividing n-butyl methacrylate, methacrylic acid and hydroxyethyl acrylate into a base material and a dropwise adding material with a mass ratio of 1:2, dividing dibenzoyl peroxide into a base material, a dropwise adding material and a supplemented material with a mass ratio of 1.5;
a) Adding n-butyl methacrylate, methacrylic acid, hydroxyethyl acrylate, dibenzoyl peroxide and ethyl acetate in the bottom material part into a reaction kettle, stirring and heating up, uniformly stirring until reflux occurs, then heating up to 90 ℃ reaction temperature, stirring and preserving heat for 1.5 hours;
b) After the heat preservation is finished, injecting the n-butyl methacrylate, the methacrylic acid, the hydroxyethyl acrylate, the dibenzoyl peroxide and the ethyl acetate of the dropwise adding material part into a titration tank to start dropwise adding, keeping the reaction temperature under stirring, and finishing dropwise adding within 4 hours;
c) After the dropwise addition, adding the dibenzoyl peroxide and the ethyl acetate in the supplementary material part, completely adding Zhong Yunsu, preserving the heat for 2 hours, and reacting to obtain the acrylic resin liquid.
The solid content of the protective layer coating for the cold stamping film prepared in this example was 19%.
Example 2
The protective layer coating for the cold-stamping film comprises the following raw materials in parts by weight:
wherein the polyester type polyurethane resin is Lu Borun polyester type polyurethane resin TPU5713, the carboxyl content of the carboxyl ternary vinyl chloride-acetate copolymer is 3%, the hydroxyl content of the hydroxyl ternary vinyl chloride-acetate copolymer is 2%, and the specific surface area of the fumed silica is 120-150m 2 The grain diameter is 12-25nm, and the dispersant is acrylate dispersant.
The preparation method of the protective layer coating for the cold stamping film comprises the following steps:
1) Preparing acrylic resin liquid;
2) Preparing coating mother liquor: weighing 16 parts of acrylic resin liquid prepared in the step 1), 10 parts of polyester type polyurethane resin, 3 parts of carboxyl ternary vinyl chloride-acetate copolymer resin, 3 parts of hydroxyl ternary vinyl chloride-acetate copolymer resin, 4 parts of fumed silica, 0.2 part of dispersing agent, 40 parts of ethyl acetate, 6 parts of methyl acetate and 10 parts of butanone, stirring uniformly and wetting, continuing stirring for 2 hours, and standing for 2 hours to obtain coating mother liquid;
3) Preparing a protective layer coating for the cold stamping film: and 2) stirring the coating mother liquor obtained in the step 2) and the rest of ethyl acetate, methyl acetate and butanone uniformly, wetting, continuing stirring for 1h, and standing for 1h to obtain the protective layer coating for the cold-stamping film.
The acrylic resin liquid is prepared from the following components in parts by weight:
the preparation method of the acrylic resin liquid of this example is as follows:
dividing n-butyl methacrylate, methacrylic acid and hydroxyethyl acrylate into the following components in a mass ratio of 1:1, dividing dibenzoyl peroxide into a base material, a dropping feed and a supplementing feed in a mass ratio of 1;
a) Adding n-butyl methacrylate, methacrylic acid, hydroxyethyl acrylate, dibenzoyl peroxide and ethyl acetate in the bottom material part into a reaction kettle, stirring and heating up, uniformly stirring until reflux begins to time, then heating up to 90 ℃, stirring and keeping the temperature for 1.5 hours;
b) After the heat preservation is finished, injecting the n-butyl methacrylate, the methacrylic acid, the hydroxyethyl acrylate, the dibenzoyl peroxide and the ethyl acetate of the dropwise adding material part into a titration tank to start dropwise adding, keeping the reaction temperature under stirring, and finishing dropwise adding within 4 hours;
c) After the dropwise addition, adding the dibenzoyl peroxide and the ethyl acetate in the supplementary material part, completely adding Zhong Yunsu, preserving the heat for 2 hours, and reacting to obtain the acrylic resin liquid.
The solid content of the protective layer coating for the cold stamping film prepared in this example was 20%.
Example 3
The protective layer coating for the cold-stamping film comprises the following raw materials in parts by weight:
wherein the polyester type polyurethane resin is Lu Borun polyester type polyurethane resin TPU5712, the carboxyl content of carboxyl ternary vinyl chloride-vinyl acetate copolymer is 3%, the hydroxyl content of hydroxyl ternary vinyl chloride-vinyl acetate copolymer is 2%, and the specific surface area of fumed silica is 120-150m 2 The grain diameter is 12-25nm, and the dispersant is phosphate type high molecular polymer dispersant.
The preparation method of the protective layer coating for the cold stamping film comprises the following steps of:
1) Preparing acrylic resin liquid;
2) Preparing coating mother liquor: weighing 14 parts of acrylic resin liquid prepared in the step 1), 6 parts of polyester type polyurethane resin, 4 parts of carboxyl ternary vinyl chloride-acetate resin, 4 parts of hydroxyl ternary vinyl chloride-acetate resin, 3 parts of fumed silica, 0.1 part of dispersing agent, 40 parts of ethyl acetate, 10 parts of methyl acetate and 10 parts of butanone, stirring uniformly and wetting, continuing stirring for 2 hours, and standing for 2 hours to obtain coating mother liquid;
3) Preparing a protective layer coating for the cold stamping film: and 2) stirring the coating mother liquor obtained in the step 2) and the rest of ethyl acetate, methyl acetate and butanone uniformly, wetting, continuing stirring for 1h, and standing for 1h to obtain the protective layer coating for the cold-stamping film.
The acrylic resin liquid is prepared from the following components in parts by weight:
the preparation method of the acrylic resin liquid of this example is as follows:
dividing n-butyl methacrylate, methacrylic acid and hydroxyethyl acrylate into the following components in a mass ratio of 1:1, dividing dibenzoyl peroxide into a base material, a dropping material and a supplementing material in a mass ratio of 1;
a) Adding n-butyl methacrylate, methacrylic acid, hydroxyethyl acrylate, dibenzoyl peroxide and ethyl acetate in the bottom material part into a reaction kettle, stirring and heating up, uniformly stirring until reflux begins to time, then heating up to 90 ℃, stirring and preserving heat for 2 hours;
b) After the heat preservation is finished, injecting the n-butyl methacrylate, the methacrylic acid, the hydroxyethyl acrylate, the dibenzoyl peroxide and the ethyl acetate of the dropwise adding material part into a titration tank to start dropwise adding, keeping the reaction temperature under stirring, and finishing dropwise adding within 4 hours;
c) After the dropwise addition, adding the dibenzoyl peroxide and the ethyl acetate in the supplementary material part, completely adding Zhong Yunsu, preserving the heat for 2 hours, and reacting to obtain the acrylic resin liquid.
The solid content of the protective layer coating for the cold stamping film prepared in the example was 18%.
Example 4
The protective layer coating for the cold stamping film comprises the following raw materials in parts by weight:
wherein the polyester type polyurethane resin is Lu Borun polyester type polyurethane resin TPU5712, the carboxyl content of carboxyl ternary vinyl chloride-vinyl acetate copolymer is 4%, the hydroxyl content of hydroxyl ternary vinyl chloride-vinyl acetate copolymer is 2%, and the specific surface area of fumed silica is 120-150m 2 The particle size is 12-25nm, and the dispersant is acrylate dispersant.
The preparation method of the protective layer coating for the cold stamping film comprises the following steps:
1) Preparing acrylic resin liquid;
2) Preparing coating mother liquor: weighing 12 parts of acrylic resin liquid prepared in the step 1), 7 parts of polyester type polyurethane resin, 4 parts of carboxyl ternary vinyl chloride-acetate resin, 4 parts of hydroxyl ternary vinyl chloride-acetate resin, 3 parts of fumed silica, 0.1 part of dispersing agent, 40 parts of ethyl acetate, 10 parts of methyl acetate and 10 parts of butanone, stirring uniformly and wetting, continuing stirring for 2 hours, and standing for 2 hours to obtain coating mother liquid;
3) Preparing a protective layer coating for the cold stamping film: and 2) stirring the coating mother liquor obtained in the step 2) and the rest of ethyl acetate, methyl acetate and butanone uniformly, wetting, continuing stirring for 1h, and standing for 1h to obtain the protective layer coating for the cold-stamping film.
The acrylic resin liquid is prepared from the following components in parts by weight:
the preparation method of the acrylic resin liquid of this example is as follows:
dividing n-butyl methacrylate, methacrylic acid and hydroxyethyl acrylate into the following components in a mass ratio of 1:1, dividing dibenzoyl peroxide into a base material, a dropping material and a supplementing material in a mass ratio of 1;
a) Adding n-butyl methacrylate, methacrylic acid, hydroxyethyl acrylate, dibenzoyl peroxide and ethyl acetate in the bottom material part into a reaction kettle, stirring and heating up, uniformly stirring until reflux begins to time, then heating up to 90 ℃, stirring and preserving heat for 2 hours;
b) After the heat preservation is finished, injecting the n-butyl methacrylate, the methacrylic acid, the hydroxyethyl acrylate, the dibenzoyl peroxide and the ethyl acetate of the dropwise adding material part into a titration tank to start dropwise adding, keeping the reaction temperature under stirring, and finishing dropwise adding within 4 hours;
c) After the dropwise addition, adding the dibenzoyl peroxide and the ethyl acetate in the supplementary material part, completely adding Zhong Yunsu, preserving the heat for 2 hours, and reacting to obtain the acrylic resin liquid.
The solid content of the protective layer coating for the cold stamping film prepared in this example was 19%.
Example 5
The protective layer coating for the cold-stamping film comprises the following raw materials in parts by weight:
wherein the polyester type polyurethane resin is Lu Borun polyester type polyurethane resin TPU5712, the carboxyl content of carboxyl ternary vinyl chloride-vinyl acetate copolymer is 4%, the hydroxyl content of hydroxyl ternary vinyl chloride-vinyl acetate copolymer is 2%, and the specific surface area of fumed silica is 120-150m 2 The particle size is 12-25nm, and the dispersant is acrylate dispersant.
The preparation method of the protective layer coating for the cold stamping film comprises the following steps:
1) Preparing acrylic resin liquid;
2) Preparing coating mother liquor: weighing 10 parts of acrylic resin liquid prepared in the step 1), 8 parts of polyester type polyurethane resin, 4 parts of carboxyl ternary vinyl chloride-acetate resin, 4 parts of hydroxyl ternary vinyl chloride-acetate resin, 3 parts of fumed silica, 0.2 part of dispersing agent, 40 parts of ethyl acetate, 10 parts of methyl acetate and 10 parts of butanone, stirring uniformly and wetting, continuing stirring for 2 hours, and standing for 2 hours to obtain coating mother liquid;
3) Preparing a protective layer coating for the cold stamping film: and 2) stirring the coating mother liquor obtained in the step 2) and the rest of ethyl acetate, methyl acetate and butanone uniformly, wetting, continuing stirring for 1h, and standing for 1h to obtain the protective layer coating for the cold-stamping film.
The acrylic resin liquid is prepared from the following components in parts by weight:
the preparation method of the acrylic resin liquid of this example is as follows:
dividing n-butyl methacrylate, methacrylic acid and hydroxyethyl acrylate into the following components in a mass ratio of 1:2, dividing dibenzoyl peroxide into a bottom material, a dropping material and a supplementing material in a mass ratio of 1;
a) Adding n-butyl methacrylate, methacrylic acid, hydroxyethyl acrylate, dibenzoyl peroxide and ethyl acetate in the bottom material part into a reaction kettle, stirring and heating up, uniformly stirring until reflux begins to time, then heating up to 90 ℃, stirring and preserving heat for 2 hours;
b) After the heat preservation is finished, injecting the n-butyl methacrylate, the methacrylic acid, the hydroxyethyl acrylate, the dibenzoyl peroxide and the ethyl acetate of the dropwise adding material part into a titration tank to start dropwise adding, keeping the reaction temperature under stirring, and finishing dropwise adding within 4 hours;
c) After the dropwise addition, adding the dibenzoyl peroxide and the ethyl acetate in the supplementary material part, completely adding Zhong Yunsu, preserving the heat for 2 hours, and reacting to obtain the acrylic resin liquid.
The solid content of the protective layer coating for the cold stamping film prepared in this example was 19%.
Example 6
The present example is different from example 1 in that the polyester urethane resin is labeled as luobu polyester urethane resin TPU5712, and the rest is the same as example 1.
Example 7
This example is different from example 1 in that the polyester urethane resin is of a Desmodium type 530, and the rest is the same as example 1.
Example 8
This example is different from example 1 in that the carboxyl group content of the carboxyl group-containing trichloroacetic resin was 3%, and the other examples are the same as example 1.
Example 9
This example is different from example 1 in that the carboxyl group content of the carboxyl group-containing trichloro-vinyl acetate terpolymer was 4%, and the other examples were the same as example 1.
Example 10
This example is different from example 1 in that the hydroxyl group content of the hydroxyl-group-containing trichloroacetic resin was 2.2%, and the rest was the same as example 1.
Example 11
The difference between the present example and example 1 is that the fumed silica has a specific surface area of 150m 2 (iv)/g, particle size 25nm, the rest of the same as example 1.
Example 12
This example is different from example 1 in that the dispersant was replaced with a phosphate type high molecular polymer dispersant, and the rest was the same as example 1.
Example 13
The present example is different from example 1 in that the synthesis ratio of the acrylic resin is replaced by: 40 parts of n-butyl methacrylate, 9 parts of methacrylic acid, 7 parts of hydroxyethyl acrylate, 0.3 part of dibenzoyl peroxide, 50 parts of ethyl acetate, the rest being identical to those of example 1.
Example 14
This example is different from example 1 in that the carboxyl group content of the carboxyl group-containing trichloro-acetic resin was 1%, and the other examples were the same as example 1.
Example 15
This example is different from example 1 in that the carboxyl group content of the carboxyl group-containing trichloro-vinyl acetate terpolymer was 5%, and the other examples were the same as example 1.
Example 16
This example is different from example 1 in that the hydroxyl group content of the hydroxyl-group-containing trichloroacetic resin was 0.5%, and the rest was the same as example 1.
Example 17
This example is different from example 1 in that the hydroxyl group content of the hydroxyl-group-containing trichloroacetic resin was 6%, and the rest was the same as example 1.
Example 18
The difference between the present example and example 1 is that the fumed silica has a specific surface area of 300m 2 The rest was the same as in example 1.
Comparative example 1
This comparative example is different from example 1 in that no carboxyl-based ternary vinyl chloride-acetate copolymer was contained, and the amount of the carboxyl-based ternary vinyl chloride-acetate copolymer was reduced by adding to the acrylic resin solution to maintain the total amount of the resin constant, and the other examples were the same as example 1.
Comparative example 2
This comparative example is different from example 1 in that the hydroxy-trichloro-acetic resin is not contained, and the amount of the reduced hydroxy-trichloro-acetic resin is added to the acrylic resin solution to keep the total amount of the resin constant, and the others are the same as those of example 1.
Comparative example 3
The comparative example is different from example 1 in that no carboxyl-and hydroxyl-based ternary vinyl chloride-vinyl acetate copolymer was contained, and the amount of the carboxyl-and hydroxyl-based ternary vinyl chloride-vinyl acetate copolymer was reduced by adding to the acrylic resin solution to maintain the total amount of the resin, and the other examples were the same as example 1.
Comparative example 4
This comparative example is different from example 1 in that the acrylic resin liquid was replaced with a polyester urethane resin, and the others were the same as those of example 1.
Comparative example 5
The comparative example differs from example 1 in that fumed silica is not included, the amount of fumed silica reduced is on average added to the other components, and the rest is the same as example 1.
The method for detecting whether the acrylic resin is qualified or not comprises the following steps:
(1) Solid content test: placing the mixture in a constant-temperature oven at 150 ℃ for 30 minutes, and determining that the measurement result is qualified when the measurement result is 47% -53%;
(2) And (3) viscosity testing: the mechanical viscosity is qualified when the temperature is 25 ℃ and the mechanical viscosity is 45000-5500 cp;
(3) And (3) testing molecular weight: the molecular weight is tested by gel chromatography, and 20000-60000 is qualified;
(4) And (3) specific gravity test: 1.00-1.20g/cm 3 ；
(5) Glass transition temperature test: 25-45 ℃.
The protective layer coating for the cold stamping films prepared in the examples 1-13 and the comparative examples 1-5 is coated on the electrochemical aluminum foil, and the dry weight of the coating is 0.3-0.4g/m 2 Drying at 120-130 deg.C, and rolling. The performance was tested and the results are shown in table 1.
According to GB/T32368-2015, a high-low temperature and humidity test box with the model of HS-80A of Shanghai and Sancheng instruments science and technology Limited is adopted to carry out the test standard of high temperature and humidity resistance, a cold stamping film is coated on an electrochemical aluminum foil by using a protective layer coating to prepare a film sample with the length of 200mm and the width of 150mm, and the film sample is stacked in the high-temperature and humidity test box, and the set temperature range is 50-60 ℃, the real temperature is 80-90%, the static pressure is 2kg, and the duration is 72 hours. After the test is finished, comparing the film material sample with the film surface which is just coated and dried, if the difference between the film material sample and the film surface is not large, the surface of the film material sample is dry and not anti-sticky, the high temperature and high humidity resistance is qualified, otherwise, the film material sample is unqualified;
(II) cold wave performance test: and testing the surface hot stamping performance of the paint sample by adopting a UV curing machine of MDYA-250 model of Manda machinery. And finishing hot stamping according to a cold stamping process, and observing a hot stamping pattern left on a printing stock.
Hot stamping area: and observing the whole of the gold stamping pattern, and representing the hot stamping area of the powder foil by the percentage of the effective area of hot stamping.
Slitting performance: and observing the grid of the gold stamping pattern, and representing the hot stamping and slitting performance by the grade of the clear grid, wherein the grade of the 0.15 mm side length grid is recorded as A grade, the grade of the 0.33 mm side length grid is recorded as B grade, the grade of the 0.56 mm side length grid is recorded as C grade (qualified grade), the grade of the 1.36 mm side length grid is recorded as D grade, and the grade of the 2.5 mm side length grid is recorded as E grade.
And (3) fastness to adhesion: testing gold stamping adhesion fastness, using 3M test tape to attach and pattern gold stamping, using 2kg roller to horizontally roll for 3 times, tearing off the test tape, observing the pattern gold stamping still remained on the printing stock, and using the percentage of the remained pattern area to represent the adhesion fastness (100% represents that the tape does not stick any pattern gold stamping, the adhesion fastness is best, 0% represents that the tape sticks all the pattern gold stamping, the adhesion fastness is worst.)
Scratch resistance: and testing the scratch resistance of the surface of the gold stamping pattern by using a friction tester. The invention uses a steel wool abrasion resistance tester with model ZJ-339-GSR of Shenzhen Shenjia instruments and equipment Limited. Setting the friction pressure to be 20N and the friction speed to be 40cpm, performing back-and-forth friction on the surface of the gold stamping pattern, and recording the back-and-forth times of the sliding block when each surface begins to generate scratches.
And (3) testing the glossiness: the glossiness of the surface of the gold stamping pattern is tested by adopting a glossiness meter, the invention uses the glossiness meter with model number WGG60 of Shanghai Xinrui instrument and meter Limited, and the testing method refers to GB/T9754-2007.
TABLE 1
As can be seen from table 1, the protective layer coatings for cold stamping films prepared in examples 1 to 13 have uniform and fine film surfaces after being coated on the electrochemical aluminum foil; the high temperature and high humidity resistance reaches the standard; in the thermoprinting performance test, the thermoprinting area is 100 percent, the slitting reaches the grade B, the adhesion fastness reaches 80 to 90 percent, the scratch resistance is more than 60 times, and the gloss (60 degrees) is 50 to 65. This fully demonstrates that the protective layer coating for cold stamping film of the invention has good coating applicability and can provide good stamping property.
The carboxyl content of the carboxyl ternary vinyl chloride-acetate copolymer of examples 14 and 16 is too low, so that the integrity and adhesion of the cold wave pattern are reduced.
The carboxyl content of the carboxyl ternary vinyl chloride-acetate resin in the examples 15 and 17 is too high, so that the integrity and the slitting performance of the cold-ironing pattern are reduced.
In example 18, the fumed silica has too large specific surface area and too large particle size, which reduces the storage stability of the coating and results in reduced integrity and adhesion of the hot stamping.
Comparative examples 1, 2 and 3, which did not contain carboxyl group ternary vinyl chloride-vinyl acetate copolymer or hydroxyl group ternary vinyl chloride-vinyl acetate copolymer, were found to decrease the adhesion of the cold wave pattern.
Comparative example 4 replacement of acrylic resin liquid with polyester polyurethane resin results in poor stability of coating liquid, poor high temperature and high humidity resistance of the prepared film, and obvious reduction of cold-ironing adhesion and slitting performance.
Comparative example 5 does not contain fumed silica, which causes the surface of the coating film to be not fine and smooth, causes the high temperature and high humidity resistance of the cold stamping film to be poor, and is unfavorable for the cutting performance of hot stamping.
The present invention is illustrated by the above examples, but the present invention is not limited to the above detailed process equipment and process flow, which means that the present invention must not be implemented by the above detailed process equipment and process flow. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that, in the above embodiments, the various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present invention does not separately describe various possible combinations.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (8)
1. The protective layer coating for the cold stamping film is characterized by comprising the following components in parts by weight:
10-20 parts of acrylic resin liquid
6-12 parts of polyester type polyurethane resin
3-5 parts of carboxyl ternary vinyl chloride-vinyl acetate copolymer
3-5 parts of hydroxyl ternary vinyl chloride-vinyl acetate copolymer
2-5 parts of fumed silica
60-80 parts of ethyl acetate
10-20 parts of methyl acetate
6-18 parts of butanone
0.1-0.3 part of dispersant;
the polyester type polyurethane resin is polyester type polyurethane resin of Lubo moist TPU5702-TPU5715 series;
the specific surface area of the fumed silica is 100-140m 2 Per gram, the particle size is 10-25nm;
the dispersant is any one or a mixture of at least two of polycarboxylic acid polymer dispersant, phosphate type high molecular polymer dispersant and acrylate dispersant.
2. The protective layer coating for the cold stamping film as claimed in claim 1, wherein the acrylic resin liquid is prepared from the following components in parts by weight:
30-40 parts of n-butyl methacrylate
5-10 parts of methacrylic acid
4-8 parts of hydroxyethyl acrylate
0.1 to 0.5 portion of dibenzoyl peroxide
40-60 parts of ethyl acetate.
3. The protective layer coating for a cold-stamping film according to claim 1, wherein the carboxyl group content of the carboxyl group ternary vinyl chloride-vinyl acetate copolymer is 2-4%.
4. The protective layer coating for a cold-stamping film according to claim 1, wherein the hydroxyl group content of the hydroxyl-ternary vinyl chloride-acetate copolymer is 1.8-2.2%.
5. A method for preparing the protective layer paint for the cold stamping film according to any one of claims 1 to 4, which comprises the following steps:
1) Preparing acrylic resin liquid;
2) Preparing coating mother liquor: weighing 10-20 parts by weight of acrylic resin liquid prepared in the step 1), 6-12 parts by weight of polyester type polyurethane resin, 3-5 parts by weight of carboxyl ternary vinyl chloride-acetate copolymer resin, 3-5 parts by weight of hydroxyl ternary vinyl chloride-acetate copolymer resin, 2-5 parts by weight of fumed silica, 0.1-0.3 part by weight of dispersant, 25-40 parts by weight of ethyl acetate, 2-5 parts by weight of methyl acetate and 5-10 parts by weight of butanone, stirring uniformly and wetting, continuing stirring, and standing to obtain a coating mother liquid;
3) Preparing a protective layer coating for the cold stamping film: and 2) uniformly stirring and wetting the coating mother liquor obtained in the step 2) and the rest of ethyl acetate, methyl acetate and butanone, continuing stirring, and standing to obtain the protective layer coating for the cold-stamping film.
6. The method according to claim 5, wherein the acrylic resin liquid is prepared in step 1) as follows:
dividing n-butyl methacrylate, methacrylic acid and hydroxyethyl acrylate into two parts of a base material and a dropwise addition material with the mass ratio of (1:1) - (1:2), dividing dibenzoyl peroxide into three parts of a base material, a dropwise addition material and a supplemented material with the mass ratio of (1;
a) Adding n-butyl methacrylate, methacrylic acid, hydroxyethyl acrylate, dibenzoyl peroxide and ethyl acetate in the bottom material part into a reaction kettle, stirring and heating up, uniformly stirring until reflux begins to time, then heating up to the reaction temperature of 75-90 ℃, stirring and preserving heat for 1-1.5h;
b) After the heat preservation is finished, injecting the n-butyl methacrylate, the methacrylic acid, the hydroxyethyl acrylate, the dibenzoyl peroxide and the ethyl acetate of the dropwise adding material part into a titration tank to start dropwise adding, keeping the reaction temperature under stirring, and finishing dropwise adding within 2.5-4 h;
c) After the dropwise addition, adding the dibenzoyl peroxide and the ethyl acetate in the supplementary material part, completely adding Zhong Yunsu, preserving the heat for 1-2h, and reacting to obtain the acrylic resin liquid.
7. The use method of the protective coating for the cold stamping film as claimed in any one of claims 1 to 4, characterized in that the protective coating for the cold stamping film is coated on the electrochemical aluminum foil, dried and rolled.
8. The use method of claim 7, wherein the dry coating amount of the protective layer coating for cold stamping film is 0.3-0.4g/m 2 And the drying temperature is 100-140 ℃.
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