CN112322086B - Electrochemical aluminum coating and preparation method thereof - Google Patents
Electrochemical aluminum coating and preparation method thereof Download PDFInfo
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- CN112322086B CN112322086B CN202011073295.7A CN202011073295A CN112322086B CN 112322086 B CN112322086 B CN 112322086B CN 202011073295 A CN202011073295 A CN 202011073295A CN 112322086 B CN112322086 B CN 112322086B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
The invention relates to an electrochemical aluminum coating and a preparation method thereof. The electrochemical aluminum coating comprises the following components in parts by weight: 10-50 parts of acrylate polymer, 10-30 parts of acrylate additive, 5-20 parts of styrene-butadiene copolymer, 0-5 parts of rosin-based hyperbranched polyester, 0-5 parts of film-forming assistant, 0-2 parts of nano silicon dioxide modified acrylic resin capable of generating light transmission, 0-2 parts of dispersant and 0-2 parts of diluent. Adding an acrylate polymer, an acrylate additive, a styrene-butadiene copolymer, rosin-based hyperbranched polyester, a film-forming aid, nano silicon dioxide modified acrylic resin and a dispersing agent into a mixed solvent to obtain a resin solution; and mixing the resin solution with the toner solution, and adding a diluent to obtain the coating. Finally forming the alumite coating which can be molded at low temperature, has high mold pressing brightness and good cutting performance.
Description
Technical Field
The invention relates to the field of coatings, in particular to an electrochemical aluminum coating and a preparation method thereof.
Background
At present, most of laser mould pressing color layer materials adopt acrylate additives, and due to the specific 'hot-sticking cold-brittleness' performance, the materials are high-quality materials meeting the mould pressing process at present. However, when the single-layer metal plate is used alone, the low-temperature die pressing lines are not clear, and the plate sticking and peeling phenomena occur at high temperature.
The temperature and the pressure are main factors influencing the die pressing process, and the die pressing temperature is usually set to 190-230 ℃ according to the material performance, so that the energy consumption is high, and equipment aging is easily caused. In order to solve the series of problems in the existing high-temperature mould pressing process, part of manufacturers begin to test the low-temperature mould pressing color layer, but most of the manufacturers can not meet the requirements of slitting performance and can not thermoprint fine patterns such as lines.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to obtain an alumite coating which can be pressed at low temperature and has better cutting property.
In order to solve the technical problems, the invention provides an electrochemical aluminum coating and a preparation method thereof.
The invention provides an electrochemical aluminum coating which comprises the following components in parts by weight: 10-50 parts of acrylate polymer, 10-30 parts of acrylate additive, 5-20 parts of styrene-butadiene copolymer, 0-5 parts of rosin-based hyperbranched polyester, 0-5 parts of film-forming assistant, 0-2 parts of dispersant and 0-2 parts of diluent.
Further, the light-transmitting nano silicon dioxide modified acrylic resin comprises 0-2 parts by weight of light-transmitting nano silicon dioxide modified acrylic resin.
Further, the toner also comprises 3-6 parts of toner according to parts by weight.
Further, the acrylate polymer comprises a butyl acrylate monomer and an acrylonitrile monomer, and the molecular weight of the acrylate polymer is 30000-50000.
Further, the acrylate additive comprises methacrylate containing benzene rings and polycyclic rigid structures and derivatives thereof.
Further, the light transmittance of the nano-silica modified acrylic resin capable of generating light transmission is above 95%.
Further, the thermal deformation temperature of the styrene-butadiene copolymer is 80-130 ℃.
Further, the dispersing agent is one or more of polyester modified phosphate ester copolymer, polyurethane and polyether phosphate ester.
Further, the diluent is one or more of ethyl acetate, butanone, butyl acetate and n-propyl acetate.
Furthermore, the diluent is prepared according to the mass ratio of ethyl acetate to butanone to n-propyl acetate of 1:3-4: 3-4.
Further, the film forming auxiliary agent is one or more of nitrocellulose, vinyl chloride-acetate copolymer and cellulose acetate butyrate.
The invention also provides a preparation method of the electrochemical aluminum coating, which comprises the following steps: adding 10-50 parts by weight of acrylate polymer, 10-30 parts by weight of acrylate additive, 5-20 parts by weight of styrene-butadiene copolymer, 0-5 parts by weight of rosin-based hyperbranched polyester, 0-5 parts by weight of film-forming assistant, 0-2 parts by weight of nano silicon dioxide modified acrylic resin and 0-2 parts by weight of dispersant into a mixed solvent to obtain a resin solution;
adding 3-6 parts of toner into the butanone solution, and uniformly stirring and mixing to obtain a toner solution;
and mixing the resin solution and the toner solution, adding 0-2 parts of diluent to adjust the solid content to be 20%, stirring for 30min until the mixture is fully and uniformly mixed, and filtering to obtain the coating.
Compared with the prior art, the invention has the advantages that: the alumite coating is obtained according to the proportion of the components, the span from the thermal deformation temperature of an acrylate polymer to the dropping point temperature is large, the coating can deform at low temperature and high pressure, the acrylate additive has a relatively stable structure and weak self thermal deformation capability, needs to deform under the action of a certain external force, has poor deformation recovery capability, and is beneficial to improving the cutting performance of a hot stamping pattern, styrene-butadiene copolymer high-softening-point polystyrene provides a stationary phase, low-softening-point polybutadiene provides a mobile phase, can ensure that the deformation is generated in a certain temperature range without melting, is beneficial to forming clear lines in mould pressing, improves the brightness of a coating, rosin-based hyperbranched polyester has a three-dimensional network structure, has good solubility, is beneficial to the dispersion of toner in a system, and improves the powder falling phenomenon in the later stage of mould pressing; the film forming assistant, the dispersant and the diluent are matched with other components to finally form the alumite coating which can be molded at low temperature, has high mold pressing brightness and good slitting performance, and the mold pressing temperature can be as low as 160-190 ℃.
Drawings
The features and advantages of the present invention will be more clearly understood by reference to the accompanying drawings, which are illustrative and not to be construed as limiting the invention in any way, and in which:
FIG. 1 is a hot stamp made with different color layer materials, (A) a hot stamp made with color layer E in comparative example 1; (B) hot stamping made of color layer C in example 3.
Detailed Description
The specific embodiment provides an electrochemical aluminum coating, which comprises the following components in parts by weight: 10-50 parts of acrylate polymer, 10-30 parts of acrylate additive, 5-20 parts of styrene-butadiene copolymer, 0-5 parts of rosin-based hyperbranched polyester, 0-5 parts of film-forming assistant, 0-2 parts of dispersant and 0-2 parts of diluent, wherein 0-2 parts of transparent nano silicon dioxide modified acrylic resin can be generated; 5-10 parts of toner.
The acrylic ester polymer is prepared by copolymerizing butyl acrylate monomers and acrylonitrile monomers, the molecular weight of the acrylic ester polymer is 30000-50000, the thermal deformation temperature is 90-120 ℃, and the dropping point temperature (the lowest temperature of a material reaching a flowing state) is 180-230 ℃; the acrylate additive comprises methacrylate containing benzene rings and polycyclic rigid structures and derivatives thereof, and the heat distortion temperature of the acrylate additive is 120-150 ℃; the thermal deformation temperature of the styrene-butadiene copolymer is 80-130 ℃.
The dispersant is one or more of polyester modified phosphate ester copolymer, high molecular weight polyurethane and high molecular weight polyether phosphate ester, and the addition amount of the dispersant is very small, so that the molecular weight of the dispersant is not specifically limited; the diluent is one or more of ethyl acetate, butanone, butyl acetate and n-propyl acetate; the diluent is prepared from ethyl acetate, butanone and n-propyl acetate according to the mass ratio of 1:3-4: 3-4; the film-forming auxiliary agent is one or more of nitrocellulose, vinyl chloride-acetate copolymer and cellulose acetate butyrate; the nitrocellulose is one or more of 1/2, 1/4, 1/8 and 1/16 seconds of nitrocellulose; the light transmittance of the nano-silica modified acrylic resin capable of generating light transmission is more than 95%; the volume shrinkage rate of the acrylic resin from a molten state to a solidified state is less than or equal to 0.5 percent;
the specific embodiment also comprises a preparation method of the electrochemical aluminum coating, which comprises the following steps: adding 10-50 parts by weight of acrylate polymer, 10-30 parts by weight of acrylate additive, 5-20 parts by weight of styrene-butadiene copolymer, 0-5 parts by weight of rosin-based hyperbranched polyester, 0-5 parts by weight of film-forming assistant, 0-2 parts by weight of nano silicon dioxide modified acrylic resin and 0-2 parts by weight of dispersant into a mixed solvent to obtain a resin solution;
adding 3-6 parts of toner into the butanone solution, and uniformly stirring and mixing to obtain a toner solution;
and mixing the resin solution and the toner solution, adding 0-2 parts of diluent to adjust the solid content to be 20%, stirring for 30min until the mixture is fully and uniformly mixed, and filtering to obtain the coating. The mixed solvent may be one or more of ethyl acetate, methyl ethyl ketone, pentanone, butyl acetate, and n-propyl acetate.
The preferred method embodiments of this invention are described in detail below with reference to the accompanying drawings, which form a part hereof, and which together with the embodiments of the invention serve to explain the principles of this invention and not to limit its scope.
The diluent in the following examples is prepared according to the mass ratio of ethyl acetate to butanone to n-propyl acetate of 1:3: 3; the mixed solvent in the following examples was as ethyl acetate: the mass ratio of the butanone to the methyl ethyl ketone is 3: 1.
Example 1
A preparation method of an electrochemical aluminum coating comprises the following steps:
(1) adding 40 parts of acrylate oligomer, 10 parts of styrene-butadiene copolymer, 10 parts of acrylate additive, 2 parts of 1/2 nitrocellulose, 5 parts of rosin-based hyperbranched polyester and 0.5 part of high molecular weight polyurethane into 120 parts of mixed solvent (comprising 90 parts of ethyl acetate and 30 parts of butanone), and fully and uniformly stirring to obtain a resin solution a;
(2) adding 3 parts of toner into the butanone solution, and uniformly stirring and mixing to obtain a toner solution;
(3) and mixing the resin solution A with the toner solution, adding a diluent to adjust the solid content to be 20%, stirring for 30min until the mixture is fully mixed, and filtering to obtain a color layer A.
Example 2
A preparation method of an electrochemical aluminum coating comprises the following steps:
(1) adding 40 parts of acrylate oligomer, 10 parts of styrene-butadiene copolymer, 10 parts of low-shrinkage acrylate additive, 2 parts of 1/2 nitrocellulose, 1 part of vinyl chloride-vinyl acetate resin, 5 parts of rosin-based hyperbranched polyester and 0.5 part of high-molecular-weight polyurethane into 120 parts of mixed solvent (comprising 90 parts of ethyl acetate and 30 parts of butanone), and fully and uniformly stirring to obtain a resin solution b;
(2) adding 5 parts of toner into the butanone solution, and uniformly stirring and mixing to obtain a toner solution;
(3) and mixing the resin solution A with the toner solution, adding 2 parts of butyl acetate serving as a diluent to adjust the solid content to 20%, stirring for 30min until the mixture is fully and uniformly mixed, and filtering to obtain a color layer B.
Example 3
A preparation method of an electrochemical aluminum coating comprises the following steps:
(1) adding 10 parts of acrylate oligomer, 30 parts of styrene-butadiene copolymer, 5 parts of low-shrinkage acrylate additive, 3 parts of 1/2 nitrocellulose, 2 parts of vinyl chloride-vinyl acetate resin, 5 parts of rosin-based hyperbranched polyester, 1 part of nano silicon dioxide modified acrylic resin capable of generating light transmission and 0.5 part of high molecular weight polyurethane into 120 parts of mixed solvent (comprising 90 parts of ethyl acetate and 30 parts of butanone), and fully and uniformly stirring to obtain a resin solution c;
(2) adding 6 parts of toner into the butanone solution, and uniformly stirring and mixing to obtain a toner solution;
(3) and (3) mixing the resin solution b with the toner solution, adding 1 part of diluent ethyl acetate to adjust the solid content to be 20%, stirring for 30min until the mixture is fully and uniformly mixed, and filtering to obtain a color layer C.
Example 4
A preparation method of an electrochemical aluminum coating comprises the following steps:
(1) adding 50 parts of acrylate oligomer, 20 parts of styrene-butadiene copolymer, 10 parts of low-shrinkage acrylate additive, 1 part of 1/8 nitrocellulose, 3 parts of vinyl chloride-vinyl acetate resin, 1 part of rosin-based hyperbranched polyester, 1 part of nano silicon dioxide modified acrylic resin capable of generating light transmission and 0.5 part of high molecular weight polyurethane into 120 parts of mixed solvent (comprising 90 parts of ethyl acetate and 30 parts of butanone), and fully and uniformly stirring to obtain a resin solution d;
(2) adding 4 parts of toner into the butanone solution, and uniformly stirring and mixing to obtain a toner solution;
(3) and (3) mixing the resin solution b with the toner solution, adding 1 part of diluent to adjust the solid content to be 20%, stirring for 30min until the mixture is fully mixed, and filtering to obtain a color layer D.
And (3) related detection test:
the heat distortion temperature and dropping point temperature of the above examples and comparative examples were measured, and the results are shown in Table 1.
TABLE 1 Heat distortion temperature and dropping Point of the above examples and comparative examples
| Heat distortion temperature/. degree.C | Dropping Point temperature/. degree.C | |
| Color layer A | 112 | Over 250 of |
| Color layer B | 105 | Over 250 of |
| Color layer C | 110 | Over 250 of |
| Color layer D | 114 | Over 250 of |
Evenly coating the color layer material on an alumite release layer through a coating machine, wherein the temperature of an oven is set as follows: the temperature is increased gradually at 80 ℃, 100 ℃, 120 ℃, 145 ℃, 150 ℃ and 130 ℃ (generally, in order to ensure that the coating is fully dried and the condition of 'external dry and internal wet' does not occur, the temperature is properly reduced at the rear section of an oven in order to avoid the phenomenon of reverse adhesion caused by overhigh temperature in the process of rolling the membrane belt, and the general design principle is low → high → low, and the temperature is properly adjusted according to the specific volatilization rate and boiling point of a solvent). And (3) preparing the alumite gold stamping foil by mould pressing (mould pressing temperature is 160-190 ℃), adopting the procedures of vacuum aluminizing, gluing and the like in the existing means, and carrying out hot stamping inspection on the slitting property, wherein the detection result is shown in table 2. The ordering of the effects from poor to good is: poor, normal, good and excellent. And with the combination of figure 1, the hot stamping prepared by the invention is clearer, the brightness is better, the hot stamping and cutting performance is better, and the plate sticking phenomenon is avoided.
TABLE 2 slitting Properties of the alumite bronzing foils prepared in comparative examples and examples
| Die pressing plate sticking condition | Die pressing brightness | Thermoprinting and cutting performance (Standard Scald)Head) | |
| Color layer A | Non-sticking plate | High brightness and clear pattern | The fuzzy area of the small square is more than 50 percent |
| Color layer B | Non-sticking plate | High brightness and clear pattern | The fuzzy area of the small squares is more than 10 percent and less than 50 percent |
| Color layer C | Non-sticking plate | High brightness and clear pattern | The fuzzy area of the small square is less than 5 percent |
| Color layer D | Non-sticking plate | High brightness and clear pattern | The fuzzy area of the small square is less than 5 percent |
The laser alumite color layer material can be molded at low temperature, and has high mold pressing brightness and good slitting performance.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (8)
1. The electrochemical aluminum coating is characterized by comprising the following components in parts by weight: 10-50 parts of acrylate polymer, 10-30 parts of acrylate additive, 5-20 parts of styrene-butadiene copolymer, 1-5 parts of rosin-based hyperbranched polyester, 0-5 parts of film-forming assistant, 0.5-2 parts of dispersant and 1-2 parts of diluent; the acrylate polymer is formed by copolymerizing a butyl acrylate monomer and an acrylonitrile monomer, and has the molecular weight of 30000-50000, the heat deformation temperature of 90-120 ℃ and the dropping point temperature of 180-230 ℃; the acrylate additive comprises methacrylate containing benzene rings and polycyclic rigid structures and derivatives thereof, and the heat distortion temperature of the acrylate additive is 120-150 ℃; the thermal deformation temperature of the styrene-butadiene copolymer is 80-130 ℃.
2. The alumite coating as claimed in claim 1, further comprising 0-2 parts by weight of a light-transmitting nanosilica modified acrylic resin.
3. The alumite coating according to claim 1 or 2, further comprising 3-6 parts by weight of a toner.
4. The alumite coating as claimed in claim 2, wherein the light transmittance of the nanosilica modified acrylic resin capable of generating light transmittance is 95% or more.
5. The alumite coating according to claim 1, wherein the diluent is one or more of ethyl acetate, methyl ethyl ketone, butyl acetate and n-propyl acetate.
6. The electrochemical aluminum paint according to claim 5, wherein the diluent is prepared according to the mass ratio of ethyl acetate to butanone to n-propyl acetate of 1:3-4: 3-4.
7. The alumite coating according to claim 1, wherein the film forming aid is one or more of nitrocellulose, a vinyl chloride-acetate resin and cellulose acetate butyrate.
8. A method for preparing an electrochemical aluminum coating according to any one of claims 1 to 7, comprising: adding 10-50 parts by weight of acrylate polymer, 10-30 parts by weight of acrylate additive, 5-20 parts by weight of styrene-butadiene copolymer, 1-5 parts by weight of rosin-based hyperbranched polyester, 1-5 parts by weight of film-forming assistant, 0-2 parts by weight of nano silicon dioxide modified acrylic resin and 0.5-2 parts by weight of dispersant into a mixed solvent to obtain a resin solution;
adding 3-6 parts of toner into the butanone solution, and uniformly stirring and mixing to obtain a toner solution;
and mixing the resin solution and the toner solution, adding 1-2 parts of diluent to adjust the solid content to be 20%, stirring for 30min until the mixture is fully and uniformly mixed, and filtering to obtain the coating.
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| CN116656199A (en) * | 2023-05-24 | 2023-08-29 | 广东邦固化学科技有限公司 | Low-temperature fast-curing common electrochemical aluminum color layer coating and preparation method thereof |
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