CN115595056B - Alumite water-based color layer coating for realizing high-speed coating and preparation method thereof - Google Patents
Alumite water-based color layer coating for realizing high-speed coating and preparation method thereof Download PDFInfo
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Abstract
The application discloses an alumite water-based color layer coating for realizing high-speed coating and a preparation method thereof, belonging to the field of alumite. An alumite water-based color layer coating for realizing high-speed coating comprises the following raw materials: 5-25% of a water-based closed isocyanate curing agent, 20-40% of a water-based polyurethane emulsion, 10-30% of modified silica sol, 0.5-2% of a water-based leveling wetting agent, 0.1-1% of a water-based defoaming agent and water; raw materials of the modified silica sol: the weight ratio of the aqueous silica sol, the bisphenol A diglycidyl ether, the polyethylene glycol monomethyl ether, the accelerant and the chitosan is 1 (0.08 to 0.16): (0.15 to 0.25): (0.001 to 0.005): 0.02 to 0.05). The application has the effect of reducing the pollution to the environment while obtaining the color layer with good performance.
Description
Technical Field
The application relates to the field of electrochemical aluminum, in particular to an electrochemical aluminum water-based color layer coating for realizing high-speed coating and a preparation method thereof.
Background
The electrochemical aluminum technology is one of packaging technologies, has a strong metal sense effect, can replace gold powder, copper powder and silver powder, is widely applied to the field of packaging industry, is often applied to packaging boxes such as cigarette boxes, wine boxes and the like, and enables the surfaces of the packaging boxes to present various marks, patterns or characters, thereby improving the appearance of the packaging boxes.
The electrochemical aluminum film generally comprises a film, a release layer, a color layer, an aluminum plating layer and an adhesive layer, wherein the film serves as a carrier, the color layer and the aluminum plating layer can be used for displaying patterns or presenting marks, the adhesive layer is used for bonding the electrochemical aluminum film to a printing stock, the release layer has the function of enabling the color layer to be rapidly separated from the film and transferred to the printing stock, and the performance of the color layer has an important influence on the stability of the electrochemical aluminum film.
The color layer is formed by coating, drying and curing the coating, and the prior color layer coating usually uses acetone or ethyl acetate organic solvent as diluent in order to obtain good dispersibility and good curing effect and further obtain a color layer with good cutting property and temperature resistance, but the diluent causes certain pollution to the environment and is difficult to meet the requirement of green production.
Disclosure of Invention
In order to reduce the pollution to the environment while obtaining a color layer with good performance, the application provides an alumite water-based color layer coating for realizing high-speed coating and a preparation method thereof.
In a first aspect, the alumite water-based color layer coating for realizing high-speed coating provided by the application adopts the following technical scheme:
an alumite water-based color layer coating for realizing high-speed coating comprises the following raw materials in percentage by weight:
5 to 25 percent of water-based closed isocyanate curing agent;
20-40% of an aqueous polyurethane emulsion;
10 to 30 percent of modified silica sol;
0.5 to 2 percent of water-based leveling wetting agent;
0.1 to 1 percent of water-based defoaming agent;
22 to 44 percent of water;
the preparation raw materials of the modified silica sol comprise aqueous silica sol, bisphenol A diglycidyl ether, polyethylene glycol monomethyl ether, an accelerator and chitosan, wherein the weight ratio of the aqueous silica sol, the bisphenol A diglycidyl ether, the polyethylene glycol monomethyl ether, the accelerator and the chitosan is 1 (0.08-0.16): (0.15-0.25): (0.001-0.005): 0.02-0.05), and the solid content of the aqueous silica sol is 20-30%.
By adopting the technical scheme, the waterborne polyurethane is used as a basic frame of the color layer, the silica sol is matched for mixing and dispersing, and the crosslinking reaction is realized between the waterborne blocked isocyanate curing agent and the silicon hydroxyl in the silica sol after high-temperature deblocking, so that a new crosslinking system is formed on the color layer besides the waterborne polyurethane, and the stability of the color layer is improved; furthermore, the silica sol is modified silica sol, bisphenol A diglycidyl ether and polyethylene glycol monomethyl ether are crosslinked to form a reinforced skeleton, chitosan is doped in the reinforced skeleton, and amino groups of the chitosan and silicon hydroxyl groups in the silica sol form hydrogen bond connection, so that a plurality of crosslinking systems are formed in a color layer in a staggered manner, the wear resistance is greatly improved, the crosslinking reaction of the water-based closed isocyanate curing agent and the silica sol and the crosslinking reaction of the chitosan and the silica sol can be quickly carried out, the color layer coating can be fully cured in a short time, the slitting performance and the temperature resistance are also improved, the coating speed of the color layer coating can be improved, and the production efficiency is improved; in addition, the raw materials are basically dissolved in water or dispersed in water, and acetone or ethyl acetate is not required to be added as a diluent, so that the pollution is less and the environment is friendly.
Optionally, the raw materials for preparing the water-based closed isocyanate curing agent comprise toluene-2,4-diisocyanate, ethylene glycol diglycidyl ether, a catalyst, N-methyldiethanolamine, methyl ethyl ketoxime and acetic acid, wherein the weight ratio of the toluene-2,4-diisocyanate, the ethylene glycol diglycidyl ether, the catalyst, the N-methyldiethanolamine, the methyl ethyl ketoxime and the acetic acid is 1 (0.5) - (0.54) (0.01) - (0.03) (0.18) - (0.22) (0.28) - (0.31) (0.1) - (0.12).
By adopting the technical scheme, N-methyldiethanolamine carries out hydrophilic modification on toluene-2,4-diisocyanate, and the prepolymerization of ethylene glycol diglycidyl ether-toluene-2,4-diisocyanate is matched to promote the crosslinking reaction rate of the aqueous closed isocyanate curing agent and silica sol, improve the crosslinking effect and improve the temperature resistance of a color layer.
Optionally, the catalyst is triethylamine.
Optionally, the chitosan is composed of O-carboxymethyl chitosan and N-carboxymethyl chitosan according to a weight ratio of 1 (0.25 to 0.4).
By adopting the technical scheme, the carboxymethyl of the O-carboxymethyl chitosan is connected with the hydroxyl, the carboxymethyl of the N-carboxymethyl chitosan is connected with the amino, and the proportion of the hydroxyl and the amino in the carboxymethyl chitosan can be controlled by controlling the proportion of the O-carboxymethyl chitosan and the N-carboxymethyl chitosan, so that the stable hydrogen bonding is formed among the chitosan, the silicon hydroxyl, the epoxy resin and the polyethylene glycol monomethyl ether, and the stability and the wear resistance of the color layer are improved.
Optionally, the average molecular weight of the polyethylene glycol monomethyl ether is 1000 to 1200.
By adopting the technical scheme, the average molecular weight of the polyethylene glycol monomethyl ether is controlled, and the color layer with high curing speed and stability is obtained.
Optionally, the aqueous silica sol is a nanoscale aqueous silica sol, and the particle size is 10 to 50nm.
By adopting the technical scheme, the water-based silica sol with the particle size within the range has rich silicon hydroxyl content, and is beneficial to the cross-linking reaction with the water-based closed isocyanate curing agent.
Optionally, the aqueous leveling wetting agent is selected from one or two of an aqueous organosilicon leveling agent and an acetylene glycol leveling agent.
By adopting the technical scheme, the water-based organic silicon flatting agent and the acetylene glycol flatting agent have the function of improving the appearance of the color layer, and a flat and smooth color layer is formed in the drying and curing process of the color layer coating.
Optionally, the aqueous defoaming agent is selected from one or two of an aqueous mineral oil defoaming agent and an aqueous molecular-scale defoaming agent.
By adopting the technical scheme, the aqueous mineral oil defoaming agent and the aqueous molecular defoaming agent both inhibit the generation of bubbles and further improve the stability of the color layer.
Optionally, the promoter is pyridine.
In a second aspect, the preparation method of the alumite water-based color layer coating for realizing high-speed coating provided by the application adopts the following technical scheme:
a preparation method of alumite water-based color layer coating for realizing high-speed coating comprises the following steps:
stirring and mixing bisphenol A diglycidyl ether, polyethylene glycol monomethyl ether and an ethanol aqueous solution, heating at 50-60 ℃ for 0.5-0.8 h, concentrating the reaction liquid to 40-50% of the original volume, and cooling to room temperature to obtain a cross-linked solution; stirring and mixing chitosan and water, then adding the cross-linking solution, stirring and mixing at room temperature, dropwise adding the obtained mixed solution into aqueous silica sol, and stirring for 0.5 to 1h to obtain modified silica sol;
and mixing the waterborne polyurethane emulsion and the modified silica sol, stirring uniformly, adding the waterborne leveling wetting agent and part of the waterborne defoaming agent, stirring uniformly, adding the waterborne closed isocyanate curing agent and the rest waterborne defoaming agent, stirring uniformly, and filtering to remove insoluble substances to obtain the electrochemical aluminum waterborne color layer coating.
By adopting the technical scheme, the bisphenol A diglycidyl ether and the polyethylene glycol monomethyl ether are mixed under the heating condition to form the reinforcement framework preliminarily, and then the chitosan is added at room temperature, so that the reinforcement framework preliminarily formed is beneficial to the doping stability of the chitosan, thereby improving the structural stability of the color layer.
Optionally, the preparation method of the water-based blocked isocyanate curing agent comprises the following steps:
stirring toluene-2,4-diisocyanate and a catalyst, heating to 65-75 ℃, dropwise adding ethylene glycol diglycidyl ether, continuously stirring to react for 1-2h after dropwise adding is finished, then cooling to 40-50 ℃, dropwise adding N-methyldiethanolamine, continuously stirring to react for 0.5-1h after dropwise adding is finished, heating to 50-60 ℃, dropwise adding methyl ethyl ketoxime, continuously stirring to react for 1-2h after dropwise adding is finished, then adding acetic acid, and continuously reacting for 0.5-1h to obtain the water-based closed isocyanate curing agent.
In summary, the present application has the following beneficial effects:
1. according to the method, waterborne polyurethane is used as a basic frame of a color layer, silica sol is matched for mixing and dispersing, and a crosslinking reaction is realized between a waterborne closed isocyanate curing agent and silicon hydroxyl in the silica sol after high-temperature deblocking, so that a new crosslinking system is formed on the color layer besides the waterborne polyurethane, and the stability of the color layer is improved; furthermore, the silica sol is modified silica sol, bisphenol A diglycidyl ether and polyethylene glycol monomethyl ether are crosslinked to form a reinforced skeleton, chitosan is doped in the reinforced skeleton, and amino groups of the chitosan and silicon hydroxyl groups in the silica sol form hydrogen bond connection, so that a plurality of crosslinking systems are formed in a color layer in a staggered manner, the wear resistance is greatly improved, the crosslinking reaction of the water-based closed isocyanate curing agent and the silica sol and the crosslinking reaction of the chitosan and the silica sol can be quickly carried out, the color layer coating can be fully cured in a short time, the slitting performance and the temperature resistance are also improved, the coating speed of the color layer coating can be improved, and the production efficiency is improved; in addition, the raw materials are basically dissolved in water or dispersed in water, and acetone or ethyl acetate is not required to be added as a diluent, so that the pollution is less and the environment is friendly.
2. The water-based blocked isocyanate curing agent is prepared by modifying toluene-2,4-diisocyanate with ethylene glycol diglycidyl ether, so that the water-based blocked isocyanate curing agent with better temperature resistance is obtained.
Drawings
FIG. 1 is a diagram of a stamping pattern for a slitting test in example 3.
Fig. 2 is a diagram of a stamping pattern of the slitting property test of comparative example 1.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples.
Preparation example
Preparation example 1
The water-based blocked isocyanate curing agent comprises the following raw materials:
10kg of toluene-2,4-diisocyanate, 5kg of ethylene glycol diglycidyl ether, 0.1kg of catalyst, 1.8kg of N-methyldiethanolamine, 2.8kg of methyl ethyl ketoxime and 1kg of acetic acid.
Wherein the catalyst is triethylamine.
The preparation method of the water-based blocked isocyanate curing agent comprises the following steps:
stirring toluene-2,4-diisocyanate and a catalyst, heating to 65 ℃, dropwise adding ethylene glycol diglycidyl ether, continuously stirring to react for 1h after dropwise adding is finished, then cooling to 50 ℃, dropwise adding N-methyldiethanolamine, continuously stirring to react for 0.5h after dropwise adding is finished, heating to 60 ℃, dropwise adding methyl ethyl ketoxime, continuously stirring to react for 1h after dropwise adding is finished, then adding acetic acid, and continuously reacting for 1h to obtain the water-based closed isocyanate curing agent.
Preparation example 2
The water-based blocked isocyanate curing agent comprises the following raw materials:
10kg of toluene-2,4-diisocyanate, 5.4kg of ethylene glycol diglycidyl ether, 0.3kg of catalyst, 2.2kg of N-methyldiethanolamine, 3.1kg of methyl ethyl ketoxime and 1.2kg of acetic acid.
Wherein the catalyst is triethylamine.
The preparation method of the water-based blocked isocyanate curing agent comprises the following steps:
stirring toluene-2,4-diisocyanate and a catalyst, heating to 75 ℃, dropwise adding ethylene glycol diglycidyl ether, continuously stirring to react for 1h after dropwise adding is finished, then cooling to 40 ℃, dropwise adding N-methyldiethanolamine, continuously stirring to react for 1h after dropwise adding is finished, heating to 50 ℃, dropwise adding methyl ethyl ketoxime, continuously stirring to react for 2h after dropwise adding is finished, then adding acetic acid, and continuously reacting for 0.5h to obtain the water-based closed isocyanate curing agent.
Preparation example 3
The present production example is different from production example 2 in that ethylene glycol diglycidyl ether is not included in the raw materials for producing the aqueous blocked isocyanate curing agent.
Examples
Example 1
The modified silica sol comprises the following raw materials:
10kg of aqueous silica sol, 0.8kg of bisphenol A diglycidyl ether, 1.5kg of polyethylene glycol monomethyl ether, 0.01kg of accelerator and 0.2kg of chitosan.
Wherein the solid content of the aqueous silica sol is 20%, and the particle size is 10 to 50nm.
Polyethylene glycol monomethyl ether has an average molecular weight of 1000.
The promoter is pyridine.
The chitosan is O-carboxymethyl chitosan.
The preparation method of the modified silica sol comprises the following steps:
stirring and mixing bisphenol A diglycidyl ether, polyethylene glycol monomethyl ether and 5kg of 40% ethanol aqueous solution, heating at 60 ℃ for 0.5h, concentrating the reaction liquid to 50% of the original volume, and cooling to room temperature to obtain a crosslinking solution; stirring and mixing chitosan and 1kg of water, then adding the cross-linking solution, stirring and mixing at room temperature, dropwise adding the obtained mixed solution into the aqueous silica sol, and stirring for 0.5h to obtain the modified silica sol.
An alumite water-based color layer coating for realizing high-speed coating comprises the following raw materials:
0.5kg of water-based closed isocyanate curing agent, 4kg of water-based polyurethane emulsion, 1kg of modified silica sol, 0.09kg of water-based leveling wetting agent, 0.01kg of water-based defoaming agent and 4.4kg of water.
Of these, a water-based blocked isocyanate curing agent was obtained in preparation example 1.
The aqueous polyurethane emulsion is Mitsui chemical W-5030.
The water-based leveling wetting agent is an acetylene glycol leveling agent, and creates Dynol 604.
The water-based defoaming agent is a water-based mineral oil defoaming agent, namely Surfynol DF220.
A preparation method of alumite water-based color layer coating for realizing high-speed coating comprises the following steps:
and mixing the waterborne polyurethane emulsion and the modified silica sol, stirring for 10min, adding the waterborne leveling wetting agent and part of the waterborne defoaming agent, stirring for 30min, adding the waterborne closed isocyanate curing agent and the rest waterborne defoaming agent, stirring for 10min, and filtering to remove insoluble substances to obtain the electrochemical aluminum waterborne color layer coating.
Example 2
The modified silica sol comprises the following raw materials:
10kg of aqueous silica sol, 1.6kg of bisphenol A diglycidyl ether, 2.5kg of polyethylene glycol monomethyl ether, 0.05kg of accelerator and 0.5kg of chitosan.
Wherein the solid content of the aqueous silica sol is 30 percent, and the particle size is 10 to 50nm.
Polyethylene glycol monomethyl ether has an average molecular weight of 1000.
The promoter is pyridine.
The chitosan is O-carboxymethyl chitosan.
The preparation method of the modified silica sol comprises the following steps:
stirring and mixing bisphenol A diglycidyl ether, polyethylene glycol monomethyl ether and 5kg of 40% ethanol aqueous solution, heating at 50 ℃ for 0.8h, concentrating the reaction liquid to 40% of the original volume, and cooling to room temperature to obtain a crosslinking solution; stirring and mixing chitosan and 1kg of water, then adding the cross-linking solution, stirring and mixing at room temperature, dropwise adding the obtained mixed solution into the aqueous silica sol, and stirring for 1h to obtain the modified silica sol.
An alumite water-based color layer coating for realizing high-speed coating comprises the following raw materials:
2.5kg of water-based closed isocyanate curing agent, 2kg of water-based polyurethane emulsion, 3kg of modified silica sol, 0.2kg of water-based leveling wetting agent, 0.1kg of water-based defoaming agent and 2.2kg of water.
Of these, a water-based blocked isocyanate curing agent was obtained in preparation example 1.
The water-based leveling and wetting agent is a water-based organic silicon leveling agent Digao Glide B1484.
The water-based defoaming agent is a water-based molecular defoaming agent winning Surfynol DF-110L.
A preparation method of alumite water-based color layer coating for realizing high-speed coating comprises the following steps:
and mixing the waterborne polyurethane emulsion and the modified silica sol, stirring for 5min, adding the waterborne leveling wetting agent and half of the total weight of the waterborne defoaming agent, stirring for 20min, adding the waterborne closed isocyanate curing agent and half of the total weight of the waterborne defoaming agent, stirring for 5min, and filtering to remove insoluble substances to obtain the electrochemical aluminum waterborne color layer coating.
Example 3
The difference between this example and example 2 is that the raw material ratio of the electrochemical aluminum water-based color layer coating is different.
Specifically, 1kg of water-based blocked isocyanate curing agent, 3kg of water-based polyurethane emulsion, 2.5kg of modified silica sol, 0.05kg of water-based leveling wetting agent, 0.05kg of water-based defoaming agent and 3.4kg of water.
Example 4
This example differs from example 3 in the source of the aqueous blocked isocyanate curing agent.
A water-based blocked isocyanate curing agent was obtained in preparation example 2.
Example 5
This example differs from example 3 in the source of the aqueous blocked isocyanate curing agent.
A water-based blocked isocyanate curing agent was obtained in production example 3.
Example 6
This example differs from example 3 in that in the preparation of the modified silica sol, the chitosan was N-carboxymethyl chitosan.
Example 7
This example differs from example 3 in that in the modified silica sol preparation method, the chitosan was O-carboxymethyl chitosan and N-carboxymethyl chitosan, the amount of O-carboxymethyl chitosan added was 0.4kg, and the amount of N-carboxymethyl chitosan added was 0.1kg.
Example 8
This example is different from example 3 in that in the preparation method of the modified silica sol, the chitosan was O-carboxymethyl chitosan and N-carboxymethyl chitosan, the amount of the O-carboxymethyl chitosan added was 0.36kg, and the amount of the N-carboxymethyl chitosan added was 0.14kg.
Example 9
This example differs from example 3 in that polyethylene glycol monomethyl ether has an average molecular weight of 1200 in the modified silica sol production method.
Example 10
This example differs from example 3 in that polyethylene glycol monomethyl ether has an average molecular weight of 1600 in the process for preparing the modified silica sol.
Example 11
This example differs from example 3 in that polyethylene glycol monomethyl ether has an average molecular weight of 750 in the process for producing the modified silica sol.
Comparative example
Comparative example 1
The comparative example is different from example 3 in that the preparation of the modified silica sol is omitted, and the same amount of aqueous silica sol is used instead of the modified silica sol in the preparation method of the alumite aqueous color layer coating.
Comparative example 2
This comparative example differs from example 3 in that, in the preparation of the modified silica sol, the methoxypolyethylene glycol was replaced by the same amount of diglycidyl ether of bisphenol A.
Comparative example 3
This comparative example differs from example 3 in that, in the preparation of the modified silica sol, the bisphenol A diglycidyl ether was replaced with an equal amount of ethylene glycol diglycidyl ether.
Comparative example 4
This comparative example differs from example 3 in that in the preparation of the modified silica sol, the same amount of carboxymethyl cellulose was used instead of O-carboxymethyl chitosan.
Performance test
Testing the blocking rate of the waterborne blocked isocyanate curing agent:
according to GB 12009.4-1989 method for measuring content of isocyanate in polymethylene polyphenyl isocyanate, initial and blocked isocyanate content in the preparation method of the water-based blocked isocyanate curing agent is tested to obtain blocking rate, and the calculation formula of the blocking rate is (initial isocyanate content-blocked isocyanate content)/initial isocyanate content multiplied by 100%, and is recorded in Table 1.
TABLE 1
| Preparation example 1 | Preparation example 2 | Preparation example 3 | |
| Blocking ratio (%) | 96.8 | 97.8 | 98.5 |
Manufacturing an electrochemical aluminum film:
the alumite aqueous color layer coating prepared in each example and comparative example of the application is mixed with dye to prepare different color layer slurry. Wherein the color layer contains 90% of paint and 10% of dye, and the dye can be water-based color concentrate.
Selecting a PET film, coating water-based wax with the solid content of 20% on the film, and drying to form a release layer; then coating the color layer slurry on a release layer with the coating weight of 1.3g/m 2 Coating speed 180m/min, drying temperature parameters: forming a color layer in a region 1 at 90 deg.C, a region 2 at 110 deg.C, a region 3 at 130 deg.C, a region 4 at 140 deg.C, and a region 5 at 110 deg.C; then aluminum plating is carried out to form an aluminum plating layer, the OD value of the aluminum plating layer is 2.1, finally, an adhesive is coated, and drying is carried out to form an adhesive layer, so that the electrochemical aluminum film is prepared.
The following tests were performed on the alumite film, in each sample of each test, the thin film, the release layer, the aluminum-plated layer, and the adhesive layer of the alumite film were kept consistent, except that the color layer slurry was prepared by different examples and comparative examples.
And (3) testing the slitting performance: and hot stamping the prepared electrochemical aluminum film to the surface of a printing stock at 125 ℃, tearing off a film, wherein the printing stock is specifically packaging paperboard, hot stamping patterns are a plurality of continuously tiled squares, and observing the appearance of the boundaries of the squares after the hot stamping is finished and recording the appearance to a table 2. The more distinct the boundary, the better the slitting performance.
And (3) testing temperature resistance: and hot stamping the prepared electrochemical aluminum film to the surface of a printing stock at 150 ℃, tearing off the film, wherein the printing stock is a packaging paperboard, the hot stamping pattern is a square pattern with the area of 50mm multiplied by 50mm, observing the glossiness of the square pattern after the hot stamping is finished, and recording the glossiness to a table 2. The brighter the gloss the better the temperature resistance.
And (3) wear resistance test: according to the 4.5.2 hot stamping layer abrasion resistance of GB 10456-1989 electrochemical aluminum hot stamping foil, the abrasion resistance of the color layer is tested, the abrasion resistance As is measured, and the record is shown in Table 2. A higher As represents a better abrasion resistance.
TABLE 2
| Test appearance of slitting Property | Gloss in 150 ℃ temperature resistance test | Abrasion resistance As (%) | |
| Example 1 | Clear boundary | High gloss and luster | 73.5 |
| Example 2 | Clear boundary | High gloss and luster | 70.8 |
| Example 3 | Clear boundary | High gloss and luster | 72.2 |
| Example 4 | Clear boundary | High gloss and luster | 70.5 |
| Example 5 | Clear boundary | Low gloss and luster | 68.1 |
| Example 6 | Clear boundary | High gloss and luster | 73.6 |
| Example 7 | Clear boundary | High gloss and luster | 81.2 |
| Example 8 | Clear boundary | High gloss and luster | 82.8 |
| Example 9 | Clear boundary | High gloss and luster | 72.5 |
| Example 10 | Clear boundary | High gloss and luster | 65.8 |
| Example 11 | Clear boundary | High gloss and luster | 64.6 |
| Comparative example 1 | Boundary bleeding and blurring | Matte luster | 47.0 |
| Comparative example 2 | Boundary bleeding and blurring | Matte luster | 49.3 |
| Comparative example 3 | Boundary bleeding and blurring | Low gloss and luster | 53.6 |
| Comparative example 4 | Clear boundary | Low gloss and luster | 56.5 |
As shown in table 2, the anodized aluminum films prepared by the anodized aluminum color layers of examples 1-4 all have good slitting property, temperature resistance and wear resistance, and the solvents used in the raw materials are mainly water and a small amount of ethanol, and do not need to use acetone or ethyl acetate, so that the environmental pollution is less, and the coating speed of the color layer coating in the process of preparing the anodized aluminum film can reach 180m/min, thereby maintaining good production efficiency and reducing energy consumption.
Specifically, as can be seen from the comparison between example 3 and comparative examples 1 to 4, compared with the common aqueous silica sol, the modified silica sol has the effects of improving the curing and stability of the color layer, promoting the improvement of the slitting performance and the temperature resistance of the electrochemical aluminum film hot stamping, and promoting the improvement of the wear resistance of the electrochemical aluminum film hot stamping due to the improvement of the stability; in addition, bisphenol A diglycidyl ether, polyethylene glycol monomethyl ether and chitosan supplement each other to form a stable reinforcing skeleton, so that the acceleration of color layer curing and the improvement of stability are promoted.
As is clear from comparison between example 3 and example 5, the gloss of the hot stamped pattern after hot stamping at 150 ℃ is higher, which indicates that the grafting effect of ethylene glycol diglycidyl ether has an influence on the aqueous blocked isocyanate curing agent and promotes the improvement of the temperature resistance of the color layer.
As can be seen from the comparison between the example 3 and the examples 6 to 8, the wear resistance As of the hot stamping pattern is higher, which indicates that the addition of O-carboxymethyl chitosan and N-carboxymethyl chitosan in the ratio of 1 (0.25 to 0.4) can promote the stability and wear resistance of the color layer to be improved.
As is clear from comparison between example 3 and examples 9 to 11, the abrasion resistance As of the hot-stamped pattern is higher, and it is demonstrated that controlling the average molecular weight of polyethylene glycol monomethyl ether to be 1000 to 1200 affects the stability of the color layer and improves the abrasion resistance of the color layer.
This detailed description is to be construed as illustrative only and is not limiting, and modifications of the detailed description, which are not inventive and may be made by persons skilled in the art after reading this description are made without departing from the spirit of the invention and within the scope of the appended claims.
Claims (8)
1. The alumite water-based color layer coating for realizing high-speed coating is characterized in that: comprises the following raw materials in percentage by weight:
5 to 25 percent of water-based closed isocyanate curing agent;
20-40% of an aqueous polyurethane emulsion;
10 to 30 percent of modified silica sol;
0.5 to 2 percent of water-based leveling wetting agent;
0.1 to 1 percent of water-based defoaming agent;
22 to 44 percent of water;
the preparation raw materials of the modified silica sol comprise aqueous silica sol, bisphenol A diglycidyl ether, polyethylene glycol monomethyl ether, an accelerator and chitosan, wherein the weight ratio of the aqueous silica sol to the bisphenol A diglycidyl ether to the polyethylene glycol monomethyl ether to the accelerator to the chitosan is 1 (0.08 to 0.16) (0.15 to 0.25) (0.001 to 0.005) to (0.02 to 0.05), and the solid content of the aqueous silica sol is 20 to 30%;
the preparation method of the alumite water-based color layer coating for realizing high-speed coating comprises the following steps:
stirring and mixing bisphenol A diglycidyl ether, polyethylene glycol monomethyl ether and an ethanol aqueous solution, heating at 50-60 ℃ for 0.5-0.8 h, concentrating the reaction liquid to 40-50% of the original volume, and cooling to room temperature to obtain a cross-linked solution; stirring and mixing chitosan and water, then adding the cross-linking solution, stirring and mixing at room temperature, dropwise adding the obtained mixed solution into aqueous silica sol, and stirring for 0.5 to 1h to obtain modified silica sol;
mixing the waterborne polyurethane emulsion and the modified silica sol, stirring uniformly, adding the waterborne leveling wetting agent and part of the waterborne defoaming agent, stirring uniformly, adding the waterborne closed isocyanate curing agent and the rest waterborne defoaming agent, stirring uniformly, and filtering to remove insoluble substances to prepare the alumite waterborne color layer coating;
the preparation method of the water-based blocked isocyanate curing agent comprises the following steps:
stirring toluene-2,4-diisocyanate and a catalyst, heating to 65-75 ℃, dropwise adding ethylene glycol diglycidyl ether, continuously stirring to react for 1-2h after dropwise adding is finished, then cooling to 40-50 ℃, dropwise adding N-methyldiethanolamine, continuously stirring to react for 0.5-1h after dropwise adding is finished, heating to 50-60 ℃, dropwise adding methyl ethyl ketoxime, continuously stirring to react for 1-2h after dropwise adding is finished, then adding acetic acid, and continuously reacting for 0.5-1h to obtain the aqueous isocyanate curing agent.
2. The alumite aqueous color layer coating for realizing high-speed coating according to claim 1, characterized in that: the preparation raw materials of the water-based closed isocyanate curing agent comprise toluene-2,4-diisocyanate, ethylene glycol diglycidyl ether, a catalyst, N-methyldiethanolamine, methyl ethyl ketoxime and acetic acid, wherein the weight ratio of the toluene-2,4-diisocyanate, the ethylene glycol diglycidyl ether, the catalyst, the N-methyldiethanolamine, the methyl ethyl ketoxime and the acetic acid is 1 (0.5) - (0.54) (0.01) - (0.03) (0.18) - (0.22) (0.28) - (0.31) (0.1) - (0.12).
3. The alumite aqueous color layer coating for realizing high-speed coating according to claim 1, characterized in that: the chitosan is composed of O-carboxymethyl chitosan and N-carboxymethyl chitosan according to the weight ratio of 1 (0.25 to 0.4).
4. The alumite aqueous color layer coating for realizing high-speed coating according to claim 1, characterized in that: the average molecular weight of the polyethylene glycol monomethyl ether is 1000 to 1200.
5. The alumite aqueous color layer coating for realizing high-speed coating according to claim 1, characterized in that: the water-based silica sol is nano-scale water-based silica sol, and the particle size is 10 to 50nm.
6. The electrochemical aluminum aqueous color layer coating for realizing high-speed coating according to claim 1, characterized in that: the water-based leveling and wetting agent is selected from one or two of a water-based organic silicon leveling agent and an acetylene glycol leveling agent.
7. The electrochemical aluminum aqueous color layer coating for realizing high-speed coating according to claim 1, characterized in that: the aqueous defoaming agent is selected from one or two of aqueous mineral oil defoaming agent and aqueous molecular defoaming agent.
8. The alumite aqueous color layer coating for realizing high-speed coating according to claim 1, characterized in that: the promoter is pyridine.
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