CN115742593A - Production process of seamless laser alcohol-resistant electrochemical aluminum and electrochemical aluminum prepared by production process - Google Patents
Production process of seamless laser alcohol-resistant electrochemical aluminum and electrochemical aluminum prepared by production process Download PDFInfo
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Abstract
The invention discloses a production process of seamless laser alcohol-resistant electrochemical aluminum and the prepared electrochemical aluminum, and relates to the field of hot stamping materials. The production process of the seamless laser alcohol-resistant electrochemical aluminum comprises the steps of coating a release coating on a base film layer to prepare a release layer; coating an imaging coating on one side of the release layer, which is far away from the base film layer, to prepare an imaging layer; pressing a pattern on the imaging layer by using soft pressing equipment; aluminizing the area corresponding to the pattern to obtain an aluminized layer; and coating an adhesive on the side of the aluminum-plated layer, which is far away from the imaging layer, and curing to obtain the seamless laser alcohol-resistant electrochemical aluminum. The imaging coating comprises a coating composition and a diluent, wherein the coating composition consists of acrylic resin polymer, vinyl chloride-vinyl acetate resin and modified monomer acrylic polymer in a specific proportion, the molecular weight range of the modified monomer acrylic polymer is 10-15 ten thousand, and the softening point temperature range is 220-240 ℃. The electrochemical aluminum prepared by the application has the effects of being seamless, good in laser effect and resistant to alcohol soaking.
Description
Technical Field
The invention relates to the field of hot stamping materials, in particular to a production process of seamless laser alcohol-resistant electrochemical aluminum and the prepared electrochemical aluminum.
Background
The seamless laser alumite is a hot stamping material prepared by coating a release layer and an imaging layer on a base film layer, then molding a laser pattern, vacuum aluminizing, coating an adhesive layer and rewinding a finished product, and is usually applied to wine covers, plastic wine boxes, daily chemical products and the like.
However, wine lids, plastic wine boxes, daily chemicals, etc. may come into contact with alcohol. At present, the following problems exist in the conventional seamless laser electrochemical aluminum:
(1) When the soft pressing equipment is used for embossing, the imaging layer with too high hardness is not suitable for mould pressing, otherwise, the laser effect is not obvious. However, to improve the moldability of alumite, it is generally necessary to add a material having high hardness and high glass transition temperature and good alcohol resistance to the image-forming layer. Therefore, when the soft pressing equipment is adopted for embossing at present, the imaging layer is generally doped with materials with relatively poor alcohol resistance, otherwise, an obvious laser effect is difficult to obtain. Therefore, the alumite prepared by the soft pressing equipment at present is generally not resistant to alcohol or can be wiped by alcohol without fading, but is easy to fade after being soaked by alcohol and has poor adhesive force.
(2) When the insert plate type hard pressing equipment is used for embossing, the imaging layer with higher hardness can be subjected to mould pressing, the obtained electrochemical aluminum can resist alcohol, the laser effect of the plate surface is good, the defects are obvious, transverse interference grains or white cracks with the width of 3-7mm are easily generated at the plate seam joint part of each period of the product, and the appearance is poor.
Therefore, how to obtain the alumite which has good laser effect and is resistant to alcohol soaking and does not generate interference fringes or cracks has important research significance.
Disclosure of Invention
In order to obtain seamless, the good and resistant alcohol soaked electrochemical aluminium of radium-shine effect, this application provides a production technology of seamless radium-shine resistant alcohol electrochemical aluminium and electrochemical aluminium who makes thereof.
The application provides a production technology of seamless radium-shine resistant alcohol electrochemical aluminium adopts following technical scheme:
a production process of seamless laser alcohol-resistant electrochemical aluminum comprises the following steps:
coating a release coating on the base film layer, and curing and forming to obtain a release layer;
coating an imaging coating on one side of the release layer, which is far away from the base film layer, and curing to obtain an imaging layer;
molding a pattern on the imaging layer by using soft pressing equipment, wherein the molding temperature is controlled at 172-180 ℃;
plating aluminum on the area corresponding to the pattern to obtain an aluminum plated layer;
coating an adhesive on one side of the aluminum plating layer, which is far away from the imaging layer, and curing to obtain seamless laser alcohol-resistant alumite;
wherein the imaging coating comprises 15-25 parts by weight of coating composition and 75-85 parts by weight of diluent, the coating composition consists of 67-73wt% of acrylic resin polymer, 7-10wt% of vinyl chloride-vinyl acetate copolymer and 20-23wt% of modified monomer acrylic polymer, the molecular weight range of the modified monomer acrylic polymer is 10-15 ten thousand, and the softening point temperature range is 220-240 ℃.
Firstly, the coating composition which can be molded by soft pressing equipment is obtained by matching the acrylic resin polymer and the modified monomer acrylic polymer in a specific ratio, and the imaging coating prepared from the coating composition can be pressed into obvious patterns by the soft pressing equipment, so that the alumite has an obvious laser effect. Meanwhile, the imaging layer is molded by adopting soft pressing equipment, so that the imaging layer is not easy to crack, and seamless alumite can be obtained.
Secondly, the problem of poor alcohol soaking resistance of an imaging layer when the acrylic resin polymer is singly adopted as the imaging coating is also solved through the matching of the acrylic resin polymer and the modified monomer acrylic polymer.
In addition, the addition of the vinyl chloride-vinyl acetate copolymer to the coating composition can enhance the bonding strength between the layers.
Optionally, the preparation method of the modified monomer acrylic acid polymer is as follows:
adding 20-30 parts by weight of polyether polyol, 60-80 parts by weight of isocyanate and 0.1-0.2 part by weight of chain extension crosslinking agent into 50-60 parts by weight of acetone, heating to 70-80 ℃, carrying out heating reflux reaction for 2-3h, then adding 3-6 parts by weight of triethylamine, stirring uniformly, adding 200-300 parts by weight of water, and dispersing uniformly to obtain a modifier;
uniformly mixing 50-60 parts by weight of modifier, 90-100 parts by weight of acrylic monomer and 100 parts by weight of acetone, then adding 1-2 parts by weight of amine chain extender and 0.5-1.2 parts by weight of initiator, heating to 70-80 ℃, carrying out reflux reaction for 2-3h, and then carrying out reduced pressure distillation to remove acetone in a reaction system, thus obtaining the modified monomer acrylic polymer.
Preferably, the isocyanate is carbodiimide-modified diphenylmethane diisocyanate, and the acrylic monomer is trifluoroethyl methacrylate.
When the isocyanate is carbodiimide modified diphenylmethane diisocyanate and the acrylic monomer is trifluoroethyl methacrylate, the imaging layer has good flexibility and temperature resistance, and the bonding fastness of the imaging layer and the aluminum plating layer is further enhanced.
Optionally, the release coating, the imaging coating and the adhesive are cured in an arc temperature mode.
The release coating is dried by an oven, the oven is divided into five zones, wherein the first zone is controlled to be 80-85 ℃, the second zone is controlled to be 100-110 ℃, the third zone is controlled to be 135-140 ℃, the fourth zone is controlled to be 135-140 ℃ and the fifth zone is controlled to be 100-110 ℃.
The imaging coating is dried by an oven, the oven is divided into five areas, wherein the first area is controlled to be 80-85 ℃, the second area is controlled to be 120-125 ℃, the third area is controlled to be 155-160 ℃, the fourth area is controlled to be 155-160 ℃, and the fifth area is controlled to be 140-150 ℃.
The adhesive is dried by an oven, the oven is divided into five areas, wherein the first area is controlled to be 70-75 ℃, the second area is controlled to be 100-105 ℃, the third area is controlled to be 125-130 ℃, the fourth area is controlled to be 125-130 ℃, and the fifth area is controlled to be 100-105 ℃.
Adopt arc temperature mode to dry from type coating, formation of image coating and adhesive, can make the solvent or the diluent of different boiling points slowly release, if the temperature just reaches the maximum temperature at once, the surface is dry thoroughly in the twinkling of an eye, can seal the slow diluent or the solvent of volatilizing at the inlayer, can improve the problem that the product later stage probably appears foaming.
Optionally, the diluent comprises butanone and n-propyl ester, and the weight ratio of the butanone to the n-propyl ester is (4.5-5.5): 1.
the thinner is a mixture of butanone and n-propyl in a specific ratio, which is favorable for further improving the dispersibility of the imaging coating and can effectively prevent the local whitening of the imaging layer.
Optionally, the release coating comprises 1-1.2 parts by weight of water-based wax with a solid content of 20%, 10-15 parts by weight of water and 13-17 parts by weight of ethanol.
Compared with the existing release coating, the release coating prepared by adopting water-based wax, water and ethanol has the advantage of environmental protection.
Optionally, the adhesive comprises 15-25 parts by weight of a resin composition and 75-85 parts by weight of a solvent, wherein the resin composition comprises 16-20 parts by weight of vinyl chloride-vinyl acetate copolymer, 11-15 parts by weight of maleic acid, 55-60 parts by weight of acrylic resin and 10-13 parts by weight of silicon dioxide; the solvent comprises toluene and n-butanol, and the weight ratio of the toluene to the n-butanol is (2.5-3.5): 1.
the adhesive can not corrode the imaging layer, can be firmly combined with the imaging layer, can adapt to various substrates to be transferred, and can be firmly combined with various substrates to be transferred.
Optionally, in the die pressing process, two rollers are used for die pressing, and the temperature of the roller for the second die pressing is 2-3 ℃ higher than that of the roller for the first die pressing.
When two plate rollers are adopted for molding, the temperature of the second plate roller is 2-3 ℃ higher than that of the first plate roller, and the alumite with better laser effect can be obtained.
Optionally, the optical density of the aluminum plating layer is controlled to be 2.0-2.3.
The optical density of the aluminum plating layer is preferably controlled to be 2.0-2.3, which is beneficial to obtaining the electrochemical aluminum with further enhanced laser effect.
In a second aspect, the application also provides the alumite prepared by any one of the production processes, and the alumite has the advantages of being seamless, good in laser effect and resistant to alcohol soaking.
To sum up, the technical scheme of the application includes following beneficial effect at least:
(1) The application has the advantages of good electrochemical aluminum laser effect, seamless performance and alcohol soaking resistance.
(2) The bonding fastness between each layer of electrochemical aluminium of this application is strong.
(3) The electrochemical aluminum has good high and low temperature resistance.
Drawings
FIG. 1 shows an electrochemical aluminum obtained in example 1 of the present application.
Fig. 2 shows alumite obtained by performing an alcohol resistance test on example 1 of the present application.
Fig. 3 shows the alumite after the adhesion test of example 1 of the present application.
Fig. 4 shows the alumite produced in comparative example 3 of the present application.
FIG. 5 shows an electrochemical aluminum prepared in comparative example 4 of the present application.
FIG. 6 shows the alumite after completion of the alcohol resistance test in comparative example 4 of the present application.
FIG. 7 shows the alumite after the adhesion test of comparative example 4 of the present application.
Detailed Description
The present application is described in further detail below with reference to figures 1-7.
The application discloses seamless radium-shine resistant alcohol electrochemical aluminium through the cooperation of formation of image coating and mould pressing process, has solved among the correlation technique problem that electrochemical aluminium is seamless, radium-shine effectual, resistant alcohol soaking is difficult to get concurrently.
Specifically, this application uses the PET film that thickness is 12um as the resistant alcohol electrochemical aluminium of seamless laser of basal lamina production, and this resistant alcohol electrochemical aluminium's of seamless laser production technology includes following step:
s1, coating a release coating on a base film layer, and curing and forming to obtain a release layer;
s2, coating an imaging coating on one side of the release layer, which is far away from the base film layer, and curing to obtain an imaging layer;
s3, die pressing a pattern on the imaging layer by adopting soft pressing equipment, wherein the die pressing temperature is controlled at 172-180 ℃; the conveying speed of the film material is controlled at 50 m/min;
s4, aluminum plating is carried out on the area corresponding to the pattern, and an aluminum plated layer is obtained;
and S5, coating an adhesive on one side of the aluminum-plated layer, which is far away from the imaging layer, and curing to obtain the seamless laser alcohol-resistant electrochemical aluminum.
The release coating adopted in the step S1 comprises 1-1.2 parts by weight of water-based wax with the solid content of 20%, 10-15 parts by weight of water and 13-17 parts by weight of ethanol. The preparation method of the release coating comprises the following steps:
uniformly stirring ethanol and water according to the proportion to obtain a mixed solution;
and adding the water-based wax with the solid content of 20% into the mixed solution, and stirring until the water-based wax is uniformly dispersed to obtain the release coating.
Compared with the existing release coating, the release coating prepared by adopting water-based wax, water and ethanol has the advantage of environmental protection.
In addition, when the release coating is coated, a 180-mesh V-shaped roller is adopted, the coating speed is controlled at 100 m/min, and the coating dry weight is controlled at 0.045-0.065g/m 2 . And curing the release coating in an oven. Preferably, the oven is divided into five zones, wherein one zone is controlled to be 80-85 ℃, the second zone is controlled to be 100-110 ℃, the third zone is controlled to be 135-140 ℃, the fourth zone is controlled to be 135-140 ℃ and the fifth zone is controlled to be 100-110 ℃. When the film material passes through the first area and the second area, ethanol and water in the release coating are basically completely volatilized, when the film material passes through the third area and the fourth area, the release coating is solidified, and the five areas are arranged to buffer the film material to some extent, so that the problem that the film material shrinks due to rapid cooling is solved.
Adopt arc temperature mode to dry from type coating, can prevent that ethanol or water volatilize too fast before the stoving, cause the coating surface dispersion not good and the problem that the coating bleaches that arouses.
The imaging paint adopted in the step S2 comprises 15-25 parts by weight of paint composition and 75-85 parts by weight of thinner, and dye or auxiliary agent can be added according to actual needs. The auxiliary agent can be any one or a combination of a plurality of antifoaming agents, dispersing agents and wetting agents, and the doping amount of the auxiliary agent can be adjusted according to the common addition or the actual requirement.
Among the key determinants of the present application on the alcohol resistance of the alumite is the composition of the coating composition. In the present application, the coating composition consists of 67-73wt% of acrylic resin polymer, 7-10wt% of vinyl chloride-vinyl acetate copolymer and 20-23wt% of modified monomer acrylic polymer, the molecular weight of the modified monomer acrylic polymer is in the range of 10-15 ten thousand, and the softening point temperature is in the range of 220-240 ℃.
The imprinting temperature of the acrylic resin polymer is 150-155 ℃, the molecular weight of the modified monomer acrylic polymer is 10-15 ten thousand, and the softening point temperature is 220-240 ℃. Through the cooperation of acrylic resin polymer and the specific proportion of modified monomer acrylic polymer, not only improved electrochemical aluminium's resistant alcohol soaking performance, still made the formation of image layer can carry out the mould pressing through soft pressure equipment for electrochemical aluminium's radium-shine effect is not influenced, has avoided adopting hard pressure equipment to carry out the mould pressing simultaneously and has made the seam crossing of electrochemical aluminium easily produce the problem of interference line or crackle. In addition, the vinyl chloride-vinyl acetate copolymer is added, so that the bonding fastness between layers is improved.
The preparation method of the modified monomer acrylic polymer comprises the following steps:
adding 20-30 parts by weight of polyether polyol, 60-80 parts by weight of isocyanate and 0.1-0.2 part by weight of chain extension crosslinking agent into 50-60 parts by weight of acetone, heating to 70-80 ℃, carrying out heating reflux reaction for 2-3h, then adding 3-6 parts by weight of triethylamine, stirring uniformly, adding 200-300 parts by weight of water, and dispersing uniformly to obtain a modifier;
uniformly mixing 50-60 parts by weight of modifier, 90-100 parts by weight of acrylic monomer and 100 parts by weight of acetone, then adding 1-2 parts by weight of amine chain extender and 0.5-1.2 parts by weight of initiator, heating to 70-80 ℃, carrying out reflux reaction for 2-3h, and then carrying out reduced pressure distillation to remove acetone in a reaction system, thus obtaining the modified monomer acrylic polymer.
The polyether polyol has a hydroxyl value of 265 to 300mgKOH/g.
The isocyanate is selected from one or a combination of two of diphenylmethane diisocyanate and carbodiimide modified diphenylmethane diisocyanate.
The chain-extending cross-linking agent is one or a combination of more of dimethylolpropionic acid, dimethylolacetic acid and dimethylolbutyric acid.
The acrylic monomer is one or a combination of methyl methacrylate, n-butyl acrylate, n-butyl methacrylate and trifluoroethyl methacrylate.
The amine chain extender is one or a combination of two of ethyl diisopropylamine and isophorone diamine.
The initiator is any one or a combination of more of di-tert-amyl peroxide, tert-butyl peroxide and diacyl peroxide.
The molecular weight of the modified monomer acrylic polymer prepared by the raw materials and the method is 10-15 ten thousand, and the softening point temperature is 220-240 ℃.
Preferably, the isocyanate is carbodiimide modified diphenylmethane diisocyanate, and the acrylic monomer is trifluoroethyl methacrylate. Compared with the isocyanate adopting diphenylmethane diisocyanate and the acrylic monomer adopting methyl methacrylate, the isocyanate adopts carbodiimide modified diphenylmethane diisocyanate, and when the acrylic monomer adopts trifluoroethyl methacrylate, the imaging layer has good flexibility and temperature resistance, and the bonding fastness of the imaging layer and the aluminum plating layer is further enhanced.
The diluent can be butanone singly, but a mixture of butanone and n-propyl is preferred, and the weight ratio of butanone to n-propyl is (4.5-5.5): 1. the thinner is a mixture of butanone and n-propyl ester in a specific ratio, which is beneficial to further improving the dispersibility of the imaging coating and preventing the imaging coating from generating local whitening.
The preparation method of the imaging coating comprises the following steps:
taking a diluent according to a proportion, adding a dye if the dye is required, stirring for 5-10min, filtering, and then entering the next step;
step two, adding the coating composition into the filtrate obtained in the step one, and stirring until the coating composition is dissolved uniformly to obtain a premix;
and step three, adding a defoaming agent and/or a dispersing agent into the premix according to actual needs, and stirring at a stirring speed of 550-750r/min for 20-30min to obtain the imaging coating.
When the imaging coating is coated, a 220-mesh V-shaped roller ceramic plate roller is adopted, the coating speed is controlled at 80 m/min, and the coating dry weight is controlled at 1.1-1.2g/m 2 And the stability of the imaging layer is further improved.
Wherein the curing of the imaging coating is carried out in an oven. The oven is preferably divided into five zones and is operated while the imaging coating is cured. Preferably, the oven is divided into five zones, wherein one zone is controlled to be 80-85 ℃, the second zone is controlled to be 120-125 ℃, the third zone is controlled to be 155-160 ℃, the fourth zone is controlled to be 155-160 ℃, and the fifth zone is controlled to be 140-150 ℃. When the film material passes through the first area and the second area, the diluent in the imaging coating is basically completely volatilized, when the film material passes through the third area and the fourth area, the imaging coating is solidified, and the five areas are arranged to buffer the film material to some extent, so that the problem that the film material is shrunk due to rapid cooling is solved.
Wherein, adopt arc temperature mode to dry to formation of image coating, can make the diluent of different boiling points slowly release, if the first district temperature has just reached the maximum temperature, the surface is dry thoroughly in the twinkling of an eye, can seal the diluent that volatilizees slowly at the inlayer, and the product later stage probably appears foaming easily.
In the step S3, the molding process may use only one plate roller or a plurality of plate rollers for molding. When two plate rollers are adopted for carrying out the die forming, the temperature of the second plate roller is preferably 2-3 ℃ higher than that of the first plate roller, and the electro-chemical aluminum with better laser effect can be obtained.
In the step S4, the optical density of the aluminum plating layer is preferably controlled to be 2.0-2.3, which is beneficial to obtaining the electrochemical aluminum with further enhanced laser effect.
In the step S5, the adhesive comprises 15-25 parts by weight of resin composition and 75-85 parts by weight of solvent, wherein the resin composition comprises 16-20 parts by weight of vinyl chloride-vinyl acetate copolymer, 11-15 parts by weight of maleic acid, 55-60 parts by weight of acrylic resin and 10-13 parts by weight of silicon dioxide; the solvent comprises toluene and n-butanol, and the weight ratio of toluene to n-butanol is (2.5-3.5): 1.
wherein, the solvent is a composition of toluene and n-butanol, which does not cause corrosion to the imaging layer and is beneficial to the uniform dispersion of the adhesive.
When the adhesive is prepared, the resin composition and the solvent are taken according to the proportion, and then the resin composition is uniformly dispersed in the solvent to obtain the adhesive.
Adopt above-mentioned adhesive can not corrode the formation of image layer, can firmly combine with the formation of image layer, and can adapt to the multiple substrate of waiting to transfer printing, can wait to transfer printing substrate with the multiple and stabilize the combination.
In addition, when coating the adhesive, a hexagonal squeeze roll is adopted, the coating speed is controlled at 100 m/min, and the coating dry weight is controlled at 0.075-0.085g/m 2 。
And the adhesive is cured in an oven. Preferably, the oven is divided into five zones, one zone is controlled at 70-75 deg.C, two zones are controlled at 100-105 deg.C, three zones are controlled at 125-130 deg.C, four zones are controlled at 125-130 deg.C, and five zones are controlled at 100-105 deg.C. When the membrane material passes through the first zone and the second zone, the solvent in the adhesive is basically completely volatilized, when the membrane material passes through the third zone and the fourth zone, the adhesive is solidified, and the five zones are arranged to buffer the membrane material to some extent, so that the problem that the membrane material is shrunk due to rapid cooling is solved.
Wherein, adopt arc temperature mode to dry imaging paint, can make the solvent of different boiling points slowly release, if the first zone temperature has just reached the maximum temperature, the surface is dry thoroughly in the twinkling of an eye, can seal the slow solvent that volatilizees at the inlayer, and the foaming probably appears in the product later stage easily.
The present application is further illustrated below by reference to preferred preparation examples, examples and comparative examples.
Preparation example
Preparation example 1
Adding 25kg of polyether polyol with the hydroxyl value of 300mgKOH/g, 70kg of diphenylmethane diisocyanate and 0.1kg of dimethylolacetic acid into 55kg of acetone, heating to 75 ℃, carrying out reflux reaction for 2.5h, then adding 4kg of triethylamine, stirring uniformly, adding 300kg of water, and dispersing uniformly to obtain a modifier;
55kg of modifier, 100kg of trifluoroethyl methacrylate and 100kg of acetone are uniformly mixed, then 1.5kg of isophorone diamine and 0.8kg of tert-butyl hydroperoxide are added, the temperature is raised to 80 ℃, the heating reflux reaction is carried out for 2 hours, and then the acetone in the reaction system is removed by reduced pressure distillation, so as to obtain the modified monomer acrylic polymer.
Preparation example 2
Adding 25kg of polyether polyol with a hydroxyl value of 300mgKOH/g, 70kg of carbodiimide modified diphenylmethane diisocyanate and 0.1kg of dimethylolacetic acid into 55kg of acetone, heating to 75 ℃, carrying out reflux reaction for 2.5h, then adding 4kg of triethylamine, stirring uniformly, adding 300kg of water, and dispersing uniformly to obtain a modifier;
55kg of modifier, 100kg of methyl methacrylate and 100kg of acetone are uniformly mixed, then 1.5kg of isophorone diamine and 0.8kg of tert-butyl hydroperoxide are added, the temperature is raised to 80 ℃, the heating reflux reaction is carried out for 2 hours, and then the acetone in the reaction system is removed by reduced pressure distillation, so as to obtain the modified monomer acrylic polymer.
Preparation example 3
Adding 25kg of polyether polyol with a hydroxyl value of 300mgKOH/g, 70kg of carbodiimide modified diphenylmethane diisocyanate and 0.1kg of dimethylolacetic acid into 55kg of acetone, heating to 75 ℃, carrying out reflux reaction for 2.5h, then adding 4kg of triethylamine, stirring uniformly, adding 300kg of water, and dispersing uniformly to obtain a modifier;
55kg of modifier, 100kg of trifluoroethyl methacrylate and 100kg of acetone are uniformly mixed, then 1.5kg of isophorone diamine and 0.8kg of tert-butyl hydroperoxide are added, the temperature is raised to 80 ℃, heating reflux reaction is carried out for 2 hours, then reduced pressure distillation is carried out to remove acetone in the reaction system, and the modified monomer acrylic polymer is obtained.
Examples
Example 1
The production process of the seamless laser alcohol-resistant electrochemical aluminum comprises the following steps:
s1, coating a release coating on a PET base film layer by adopting a 180-mesh V-shaped roller, wherein the coating speed is controlled to be 100 m/min, and the coating dry weight is controlled to be 0.055g/m 2 Then drying, curing and molding the release coating in a drying oven to obtain a release layer, wherein the drying oven is divided into five areas, namely, a first area is controlled to be 80-85 ℃, a second area is controlled to be 100-110 ℃, a third area is controlled to be 135-140 ℃, a fourth area is controlled to be 135-140 ℃ and a fifth area is controlled to be 100-110 ℃;
s2, coating an imaging coating on one side of the release layer, which is far away from the base film layer, by adopting a 220-mesh V-shaped roller ceramic plate roller, wherein the coating speed is controlled at 80 m/min, and the coating dry weight is controlled at 1.05g/m 2 Then, drying, curing and molding the imaging coating by an oven to obtain an imaging layer, wherein the oven is divided into five areas, the first area is controlled to be 80-85 ℃, the second area is controlled to be 120-125 ℃, the third area is controlled to be 155-160 ℃, the fourth area is controlled to be 155-160 ℃, and the fifth area is controlled to be 140-150 ℃;
s3, die pressing a pattern on the imaging layer by adopting soft pressing equipment, wherein the die pressing process adopts two rollers for die pressing, the temperature of the roller for the first die pressing is controlled at 174 ℃, the temperature of the roller for the second die pressing is controlled at 176 ℃, and the conveying speed of a film material is controlled at 50 m/min;
s4, aluminum plating is carried out on the area corresponding to the pattern, and the optical density of the aluminum plating layer is 1.8, so that the aluminum plating layer is obtained;
s5, coating an adhesive on one side of the aluminum-plated layer, which is far away from the imaging layer, by adopting a hexagonal extrusion roller, wherein the coating speed is controlled to be 100 m/min, and the coating dry weight is controlled to be 0.075g/m 2 Then, the adhesive is dried, cured and formed by an oven to obtain the adhesive layer, the oven is divided into five areas, wherein the temperature of the first area is controlled to be 70-75 ℃, the temperature of the second area is controlled to be 100-105 ℃, the temperature of the third area is controlled to be 125-130 ℃, the temperature of the fourth area is controlled to be 125-130 ℃, and the temperature of the fifth area is controlled to be 100-105 ℃.
In this example, the release coating was prepared by uniformly stirring and dispersing 1kg of aqueous wax having a solid content of 20%, 10kg of water, and 13kg of ethanol.
The imaging coating was prepared by uniformly mixing 15kg of the coating composition, 75kg of the diluent, 0.08kg of the defoamer, and 0.03kg of the dispersant.
Wherein the coating composition comprises 67kg of acrylic resin polymer, 10kg of vinyl chloride-vinyl acetate copolymer and 23kg of modified monomer acrylic polymer. The acrylic resin polymer and the vinyl chloride-vinyl acetate copolymer can be directly purchased from the market. Modified monomer acrylic acid polymer the modified monomer acrylic acid polymer prepared in preparation example 1 was used. The diluent is a mixture of butanone and n-propyl ester, and the weight ratio of the butanone to the n-propyl ester is 5:1.
the adhesive was prepared by uniformly mixing 15kg of the resin composition with 85kg of the solvent. Wherein the resin composition comprises 16kg of vinyl chloride-vinyl acetate copolymer, 11kg of maleic acid, 60kg of acrylic resin and 13kg of silicon dioxide; the solvent is toluene.
Example 2
The production process of the seamless laser alcohol-resistant electrochemical aluminum is different from that of the embodiment 1 in that:
in this example, the release coating was prepared by uniformly stirring and dispersing 1.2kg of aqueous wax having a solid content of 20%, 15kg of water, and 17kg of ethanol.
The imaging coating was prepared by uniformly mixing 25kg of the coating composition, 75kg of the diluent, 0.08kg of the defoamer, and 0.03kg of the dispersant. Wherein the coating composition comprises 73kg of acrylic resin polymer, 7kg of vinyl chloride-vinyl acetate copolymer and 20kg of modified monomer acrylic polymer. Butanone is used as the diluent.
Modified monomer acrylic acid polymer the modified monomer acrylic acid polymer prepared in preparation example 1 was used.
The adhesive was prepared by uniformly mixing 25kg of the resin composition with 85kg of the solvent. Wherein the resin composition comprises 20kg of vinyl chloride-vinyl acetate copolymer, 15kg of maleic acid, 55kg of acrylic resin and 10kg of silicon dioxide; the solvent is toluene.
Example 3
The production process of the seamless laser alcohol-resistant electrochemical aluminum is different from that of the embodiment 1 in that:
modified monomer acrylic acid polymer the modified monomer acrylic acid polymer prepared in preparation example 2 was used.
Example 4
The production process of the seamless laser alcohol-resistant electrochemical aluminum is different from that of the embodiment 1 in that:
modified monomer acrylic acid polymer the modified monomer acrylic acid polymer prepared in preparation example 3 was used.
Comparative example
Comparative example 1
The production process of the seamless laser alcohol-resistant electrochemical aluminum is different from that of the embodiment 1 in that:
and (4) performing die pressing by using hard pressing equipment.
Comparative example 2
The production process of the seamless laser alcohol-resistant electrochemical aluminum is different from that of the embodiment 1 in that:
the coating composition included 20kg of acrylic polymer, 7kg of vinyl chloride-vinyl acetate copolymer, and 73kg of modified monomeric acrylic polymer.
Comparative example 3
The production process of the seamless laser alcohol-resistant electrochemical aluminum is different from that of the embodiment 1 in that:
the molding was performed using a hard press, and the coating composition included 20kg of an acrylic polymer, 7kg of a vinyl chloride-vinyl acetate copolymer, and 73kg of a modified monomer acrylic polymer.
Comparative example 4
The production process of the seamless laser alcohol-resistant electrochemical aluminum is different from that of the embodiment 1 in that: the modified monomer acrylic acid polymer used is different, in this comparative example, the molecular weight of the modified monomer acrylic acid polymer is 8.6 ten thousand, and the softening point temperature is 198 ℃.
Comparative example 5
The production process of the seamless laser alcohol-resistant electrochemical aluminum is different from that of the embodiment 1 in that: the modified monomer acrylic acid polymer used was different, in this comparative example, the molecular weight of the modified monomer acrylic acid polymer was 18.5 ten thousand, and the softening point temperature was 263 ℃.
Performance test data
(1) Testing alcoholic strength: the alumite in each of the above examples and comparative examples was hot stamped on a PET sheet, and then soaked in 53 ° alcohol for 1 hour to observe whether discoloration or decoloration occurred.
(2) And (3) testing the adhesion performance: the alumite in each of the above examples and comparative examples was hot stamped on a PET sheet, and after being soaked in alcohol of 53 degrees for 1 hour, the adhesion property of the imaging layer was tested using a 3M810 tape.
(3) The imaging layer is a coating cracking phenomenon: and (4) visually observing.
(4) And (3) laser effect: and (4) visually observing.
(5) High temperature resistance: and (4) whether the color is changed by hot stamping at the temperature of 150 ℃ or not, and the hot stamping time is delayed for 0.4s.
(6) Low temperature resistance: the alumite in each example and comparative example was hot stamped on a PET sheet, soaked in 53-degree alcohol for 1 hour, and then placed in an environment of-50 ℃ for 24 hours to test whether the imaging layer was brittle.
TABLE 1 Properties of alumite in examples 1-4 and comparative examples 1-5
Analysis of results
The difference between the comparative example 1 and the example 1 is that the equipment used for molding is different, and the data in table 1 show that the molding using the hard press equipment is easy to cause the problem of coating cracking, which is not favorable for obtaining seamless products.
The difference between the comparative example 2 and the example 1 is that the mixing amounts of the acrylic resin polymer and the modified monomer acrylic polymer in the coating composition are interchanged, and the data in table 1 show that when the mixing amount of the modified monomer acrylic polymer is increased and the molding is performed by using a soft pressing device, the laser effect of the alumite is not obvious, and the expected product cannot be obtained.
The difference between the comparative example 3 and the example 1 is that the equipment selected for die pressing is hard pressing equipment, the mixing amounts of the acrylic resin polymer and the modified monomer acrylic polymer in the coating composition are interchanged, and the data in the table 1 show that the alumite with alcohol soaking resistance and strong adhesion of an imaging layer can be obtained by using the hard pressing equipment, but the problem of coating cracking easily occurs in the alumite, and seamless alumite cannot be obtained.
The comparative examples 4 to 5 are different from example 1 in that the molecular weight and the softening point temperature of the modified monomer acrylic polymer are out of the range of the application, and it can be seen from the data in table 1 that the molecular weight and the softening point temperature of the modified acrylic monomer are out of the range of the application, which is not good for obtaining the alumite with alcohol soaking resistance, seamless performance and good laser effect.
The difference between the embodiment 4 and the embodiments 1 and 3 lies in that the raw materials of the modified monomer acrylic polymer are different, wherein the isocyanate is carbodiimide modified diphenylmethane diisocyanate, and when the acrylic monomer is trifluoroethyl methacrylate, not only can the alumite with alcohol soaking resistance, seamless performance and good laser effect be obtained, but also the low temperature resistance of the imaging layer can be improved, and the imaging layer is not easy to crack at the temperature of-50 ℃.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A production process of seamless laser alcohol-resistant electrochemical aluminum is characterized by comprising the following steps: the method comprises the following steps:
coating a release coating on the base film layer, and curing and forming to obtain a release layer;
coating an imaging coating on one side of the release layer, which is far away from the base film layer, and curing to obtain an imaging layer;
molding a pattern on the imaging layer by using soft pressing equipment, wherein the molding temperature is controlled at 172-180 ℃;
plating aluminum on the area corresponding to the pattern to obtain an aluminum plated layer;
coating an adhesive on one side of the aluminum-plated layer, which is far away from the imaging layer, and curing to obtain seamless laser alcohol-resistant electrochemical aluminum;
wherein the imaging coating comprises 15-25 parts by weight of coating composition and 75-85 parts by weight of diluent, the coating composition consists of 67-73wt% of acrylic resin polymer, 7-10wt% of vinyl chloride-vinyl acetate copolymer and 20-23wt% of modified monomer acrylic polymer, the molecular weight range of the modified monomer acrylic polymer is 10-15 ten thousand, and the softening point temperature range is 220-240 ℃.
2. The production process of the seamless laser alcohol-resistant electrochemical aluminum according to claim 1, characterized in that: the preparation method of the modified monomer acrylic polymer comprises the following steps:
adding 20-30 parts by weight of polyether polyol, 60-80 parts by weight of isocyanate and 0.1-0.2 part by weight of chain extension crosslinking agent into 50-60 parts by weight of acetone, heating to 70-80 ℃, carrying out heating reflux reaction for 2-3h, then adding 3-6 parts by weight of triethylamine, stirring uniformly, adding 200-300 parts by weight of water, and dispersing uniformly to obtain a modifier;
uniformly mixing 50-60 parts by weight of modifier, 90-100 parts by weight of acrylic monomer and 100 parts by weight of acetone, then adding 1-2 parts by weight of amine chain extender and 0.5-1.2 parts by weight of initiator, heating to 70-80 ℃, carrying out reflux reaction for 2-3h, and then carrying out reduced pressure distillation to remove acetone in a reaction system, thus obtaining the modified monomer acrylic polymer.
3. The production process of the seamless laser alcohol-resistant electrochemical aluminum according to claim 2, characterized in that: the isocyanate is carbodiimide modified diphenylmethane diisocyanate, and the acrylic monomer is trifluoroethyl methacrylate.
4. The production process of the seamless laser alcohol-resistant electrochemical aluminum according to claim 1, characterized in that: the release coating, the imaging coating and the adhesive are all cured in an arc-shaped temperature mode.
5. The production process of the seamless laser alcohol-resistant electrochemical aluminum according to claim 1, characterized in that: the diluent comprises butanone and n-propyl ester, and the weight ratio of the butanone to the n-propyl ester is (4.5-5.5): 1.
6. the production process of the seamless laser alcohol-resistant electrochemical aluminum according to claim 1, characterized in that: and in the mould pressing procedure, two rollers are adopted for mould pressing, and the temperature of the roller for the second mould pressing is 2-3 ℃ higher than that of the roller for the first mould pressing.
7. The production process of the seamless laser alcohol-resistant electrochemical aluminum according to claim 1, characterized in that: the optical density of the aluminum-plated layer is controlled to be 2.0-2.3.
8. The production process of the seamless laser alcohol-resistant electrochemical aluminum according to claim 1, characterized in that: the release coating comprises 1-1.2 parts by weight of water-based wax with the solid content of 20%, 10-15 parts by weight of water and 13-17 parts by weight of ethanol.
9. The seamless laser alcohol-resistant electrochemical aluminum according to claim 1, characterized in that: the adhesive comprises 15-25 parts of resin composition and 75-85 parts of solvent, wherein the resin composition comprises 16-20 parts of vinyl chloride-vinyl acetate copolymer, 11-15 parts of maleic acid, 55-60 parts of acrylic resin and 10-13 parts of silicon dioxide; the solvent comprises toluene and n-butanol, and the weight ratio of the toluene to the n-butanol is (2.5-3.5): 1.
10. the alcohol-resistant electrochemical aluminum produced by the seamless laser alcohol-resistant electrochemical aluminum production process of any one of claims 1 to 9.
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