CN115368798A - Electrochemical aluminum laser layer coating and preparation method thereof - Google Patents
Electrochemical aluminum laser layer coating and preparation method thereof Download PDFInfo
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- CN115368798A CN115368798A CN202210845220.9A CN202210845220A CN115368798A CN 115368798 A CN115368798 A CN 115368798A CN 202210845220 A CN202210845220 A CN 202210845220A CN 115368798 A CN115368798 A CN 115368798A
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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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
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
-
- 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 discloses an alumite laser layer coating and a preparation method thereof. The paint comprises the following components in parts by weight: 10-30 parts of isobutyl polymethacrylate resin, 10-30 parts of styrene-indene resin, 40-60 parts of solvent, 3-5 parts of cellulose nitrate and 2-8 parts of locust bean gum. The laser layer coating adopts the mixed main material of the polyisobutyl methacrylate resin and the styrene-indene resin, less permeates the isolation layer during hot stamping, the prepared electrochemical aluminum hot stamping foil has low stripping value and is beneficial to transfer printing, and the locust bean gum is added into the components, so that the adhesive force of the material is increased, and the coating is stable and is not easy to damage.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an alumite laser layer coating and a preparation method thereof.
Background
The electrochemical aluminum foil has been receiving more and more attention in the field of material packaging due to its exquisite appearance and excellent performance. The laser electrochemical aluminum usually comprises a five-layer structure, namely a substrate film, a release layer, a color layer, a vacuum aluminum-plated layer and an adhesive layer. The laser alumite coating is a core raw material for preparing an alumite hot stamping foil, is high in requirement, coating resin needs to have good film forming property and good film forming toughness, needs to have certain scratch resistance and wear resistance, and needs to have certain adhesive force to an aluminum layer after curing and good moldability.
Patent 201210115718.6 discloses a laser electrochemical aluminum coating composition and a preparation method thereof, wherein the laser electrochemical aluminum coating comprises the following components in percentage by weight: 13-28% of acrylic resin, 2-7% of cellulose nitrate resin, 0-5% of styrene maleic anhydride resin, 0-4% of aldehyde ketone resin, 0-1% of auxiliary agent and 65-80% of solvent; the preparation method comprises the following steps: putting the solvent into a reaction kettle, and heating to 40-70 ℃ while stirring; putting the cellulose nitrate resin into a reaction kettle, and stirring; sequentially putting the rest resins into the reaction kettle, and continuously stirring; and after all the added resin is completely dissolved, adding the auxiliary agent into the reaction kettle, dispersing, and cooling to obtain the laser electrochemical aluminum coating. The electrochemical aluminum coating has high stripping value and low adhesive force, and cannot meet the requirement of the laser electrochemical aluminum coating on mechanical property.
Disclosure of Invention
The invention aims to provide a laser electrochemical aluminum coating and a preparation method thereof.
An electrochemical aluminum laser layer coating comprises the following components in parts by weight: 10-30 parts of isobutyl polymethacrylate resin, 10-30 parts of styrene-indene resin, 40-60 parts of solvent, 3-5 parts of cellulose nitrate and 2-8 parts of locust bean gum.
The preparation method of the styrene-indene resin comprises the following steps:
(1) According to the weight parts, taking 10-20 parts of styrene and 5-15 parts of indene, and uniformly stirring and mixing to obtain a raw material mixed solution;
(2) Adding a catalyst into the raw material mixed solution, heating to 100-150 ℃, and reacting for 20-40min to obtain a polymerization solution;
(3) And (3) removing the catalyst in the polymerization liquid obtained in the step (2), and carrying out reduced pressure distillation on the polymerization liquid with the catalyst removed to obtain the styrene-indene resin.
The catalyst is sulfuric acid and/or phosphoric acid.
The mass of the catalyst is 1-5% of the raw material mixed liquor.
The mass ratio of the styrene to the indene is 1: (0.2-1).
The catalyst removal method comprises the following steps: adding calcium hydroxide into the polymerization solution, stirring for 30-60min until the pH of the material is 6.5-8.5, and filtering.
The reduced pressure distillation method comprises the following steps: and carrying out reduced pressure distillation on the polymerization solution from which the catalyst is removed under the conditions of vacuum degree of-0.05 to-0.10 MPa and temperature of 180-220 ℃ until unreacted raw materials are removed, and cooling to room temperature to obtain the styrene-indene resin.
The solvent is one or more of ethanol, butanone, propanol, n-butanol, ethyl acetate and n-propyl acetate.
The preparation method of the electrochemical aluminum laser layer coating comprises the steps of dissolving the polyisobutyl methacrylate resin, the styrene-indene resin, the cellulose nitrate and the locust bean gum in the solvent and stirring, wherein the stirring speed is 500-1500m/min, and the stirring time is 1-4h.
The invention has the beneficial effects that: the laser layer coating adopts the mixed main material of the polyisobutyl methacrylate resin and the styrene-indene resin, the isolating layer is less permeated in hot stamping, the stripping value of the prepared hot stamping foil of the alumite is low, transfer printing is facilitated, and the locust bean gum is added into the components, so that the adhesive force of the material is increased, and the coating is stable and is not easy to damage.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example 1
An electrochemical aluminum laser layer coating comprises the following components in parts by weight: 20 parts of polyisobutyl methacrylate resin, 20 parts of styrene-indene resin, 50 parts of ethanol, 4 parts of cellulose nitrate and 5 parts of locust bean gum.
The preparation method of the styrene-indene resin comprises the following steps:
(1) According to the weight parts, taking 15 parts of styrene and 10 parts of indene, and uniformly stirring and mixing to obtain a raw material mixed solution;
(2) Adding sulfuric acid into the raw material mixed solution, heating to 120 ℃, and reacting for 30min to obtain a polymerization solution; the mass of the sulfuric acid is 3 percent of the raw material mixed liquor;
(3) Removing sulfuric acid in the polymerization liquid obtained in the step (2), and carrying out reduced pressure distillation on the polymerization liquid with the sulfuric acid removed to obtain styrene-indene resin; the method for removing the sulfuric acid comprises the following steps: adding calcium hydroxide into the polymerization solution, stirring for 50min until the pH of the material is 7.0, and filtering; the reduced pressure distillation method comprises the following steps: and (3) carrying out reduced pressure distillation on the polymerization solution subjected to sulfuric acid removal at the vacuum degree of-0.07MPa and the temperature of 200 ℃, cooling to room temperature after removing unreacted raw materials, and thus obtaining the styrene-indene resin.
The preparation method of the electrochemical aluminum laser layer coating comprises the steps of dissolving the polyisobutyl methacrylate resin, the styrene-indene resin, the cellulose nitrate and the locust bean gum in ethanol and stirring at the stirring speed of 1000m/min for 3h.
Example 2
The electrochemical aluminum laser layer coating comprises the following components in parts by weight: 12 parts of polyisobutyl methacrylate resin, 12 parts of styrene-indene resin, 40 parts of n-butyl alcohol, 3 parts of cellulose nitrate and 2 parts of locust bean gum.
The preparation method of the styrene-indene resin comprises the following steps:
(1) According to the weight parts, taking 12 parts of styrene and 6 parts of indene, and uniformly stirring and mixing to obtain a raw material mixed solution;
(2) Adding phosphoric acid into the raw material mixed solution, heating to 110 ℃, and reacting for 40min to obtain a polymerization solution; the mass of the phosphoric acid is 5% of the raw material mixed liquor;
(3) Removing phosphoric acid in the polymerization liquid obtained in the step (2), and carrying out reduced pressure distillation on the polymerization liquid without phosphoric acid to obtain styrene-indene resin; the method for removing phosphoric acid comprises the following steps: adding calcium hydroxide into the polymerization solution, stirring for 30min until the pH of the material is 6.8, and filtering; the method for reduced pressure distillation comprises the following steps: and (3) carrying out reduced pressure distillation on the polymerization solution subjected to phosphoric acid removal at the temperature of 180 ℃ under the vacuum degree of-0.05MPa until unreacted raw materials are removed, and then cooling to room temperature to obtain the styrene-indene resin.
The preparation method of the electrochemical aluminum laser layer coating comprises the steps of dissolving the polyisobutyl methacrylate resin, the styrene-indene resin, the cellulose nitrate and the locust bean gum in n-butyl alcohol and stirring, wherein the stirring speed is 700m/min, and the stirring time is 4 hours.
Example 3
An electrochemical aluminum laser layer coating comprises the following components in parts by weight: 30 parts of polyisobutyl methacrylate resin, 30 parts of styrene-indene resin, 60 parts of n-propyl acetate, 5 parts of cellulose nitrate and 6 parts of locust bean gum.
The preparation method of the styrene-indene resin comprises the following steps:
(1) According to the weight parts, 20 parts of styrene and 15 parts of indene are taken, and are stirred and mixed uniformly to obtain a raw material mixed solution;
(2) Adding sulfuric acid into the raw material mixed solution, heating to 150 ℃, and reacting for 20min to obtain a polymerization solution; the mass of the sulfuric acid is 1% of the raw material mixed liquor;
(3) Removing sulfuric acid in the polymerization liquid obtained in the step (2), and carrying out reduced pressure distillation on the polymerization liquid with the sulfuric acid removed to obtain styrene-indene resin; the method for removing the sulfuric acid comprises the following steps: adding calcium hydroxide into the polymerization solution, stirring for 50min until the pH of the material is 7.5, and filtering; the reduced pressure distillation method comprises the following steps: and (3) carrying out reduced pressure distillation on the polymerization solution subjected to sulfuric acid removal at the vacuum degree of-0.10 MPa and the temperature of 220 ℃ until unreacted raw materials are removed, and cooling to room temperature to obtain the styrene-indene resin.
The preparation method of the electrochemical aluminum laser layer coating comprises the steps of dissolving the polyisobutyl methacrylate resin, the styrene-indene resin, the cellulose nitrate and the locust bean gum in the n-propyl acetate and stirring, wherein the stirring speed is 1500m/min, and the stirring time is 1h.
Comparative example 1
An electrochemical aluminum laser layer coating comprises the following components in parts by weight: 40 parts of polyisobutyl methacrylate resin, 50 parts of ethanol, 4 parts of cellulose nitrate and 5 parts of locust bean gum.
The preparation method of the electrochemical aluminum laser layer coating comprises the steps of dissolving the polyisobutyl methacrylate resin, cellulose nitrate and locust bean gum in ethanol and stirring, wherein the stirring speed is 1000m/min, and the stirring time is 3 hours.
Comparative example 2
An electrochemical aluminum laser layer coating comprises the following components in parts by weight: 40 parts of styrene-indene resin, 50 parts of ethanol, 4 parts of cellulose nitrate and 5 parts of locust bean gum.
The preparation method of the styrene-indene resin comprises the following steps:
(1) According to the weight parts, taking 15 parts of styrene and 10 parts of indene, and uniformly stirring and mixing to obtain a raw material mixed solution;
(2) Adding sulfuric acid into the raw material mixed solution, heating to 120 ℃, and reacting for 30min to obtain a polymerization solution; the mass of the sulfuric acid is 3 percent of the raw material mixed liquor;
(3) Removing sulfuric acid in the polymerization liquid obtained in the step (2), and carrying out reduced pressure distillation on the polymerization liquid with the sulfuric acid removed to obtain styrene-indene resin; the method for removing the sulfuric acid comprises the following steps: adding calcium hydroxide into the polymerization solution, stirring for 50min until the pH of the material is 7.0, and filtering; the reduced pressure distillation method comprises the following steps: and (3) carrying out reduced pressure distillation on the polymerization solution subjected to sulfuric acid removal at the vacuum degree of-0.07MPa and the temperature of 200 ℃, cooling to room temperature after removing unreacted raw materials, and thus obtaining the styrene-indene resin.
The preparation method of the electrochemical aluminum laser layer coating comprises the steps of dissolving styrene-indene resin, cellulose nitrate and locust bean gum in ethanol and stirring, wherein the stirring speed is 1000m/min, and the stirring time is 3 hours.
Comparative example 3
An electrochemical aluminum laser layer coating comprises the following components in parts by weight: 20 parts of polyisobutyl methacrylate resin, 20 parts of styrene-indene resin, 50 parts of ethanol and 4 parts of cellulose nitrate.
The preparation method of the styrene-indene resin comprises the following steps:
(1) According to the weight parts, taking 15 parts of styrene and 10 parts of indene, and uniformly stirring and mixing to obtain a raw material mixed solution;
(2) Adding sulfuric acid into the raw material mixed solution, heating to 120 ℃, and reacting for 30min to obtain a polymerization solution; the mass of the sulfuric acid is 3 percent of the raw material mixed liquor;
(3) Removing sulfuric acid in the polymerization liquid obtained in the step (2), and carrying out reduced pressure distillation on the polymerization liquid with the sulfuric acid removed to obtain styrene-indene resin; the method for removing the sulfuric acid comprises the following steps: adding calcium hydroxide into the polymerization solution, stirring for 50min until the pH of the material is 7.0, and filtering; the reduced pressure distillation method comprises the following steps: and (3) carrying out reduced pressure distillation on the polymerization solution subjected to sulfuric acid removal under the conditions of vacuum degree of-0.07MPa and 200 ℃, cooling to room temperature after removing unreacted raw materials, and thus obtaining the styrene-indene resin.
The preparation method of the alumite laser layer coating comprises the steps of dissolving the polyisobutyl methacrylate resin, the styrene-indene resin and the cellulose nitrate in ethanol and stirring at the stirring speed of 1000m/min for 3h.
Experimental example:
the preparation method of the alumite hot stamping foil comprises the following steps: coating a release agent (2 percent of emulsified water-based wax, 49 percent of absolute ethyl alcohol and 49 percent of deionized water) on the film base layer, printing by a 200-mesh plate roller, and coating an amount of 5.0 g/square meter to form a release layer; coating the electrochemical aluminum laser layer coating of the examples 1 to 3 and the comparative examples 1 to 3 on the isolation layer, printing by a roller with 350 meshes, coating 2.5g per square meter, coating a fluorescent agent (a fluorescent whitening agent BC), printing by a roller with 180 meshes, and coating 0.5g per square meter to form a fluorescent layer; pressing a laser pattern on the fluorescent layer to form an image, then performing an aluminum plating process, and evaporating two aluminum layers on the fluorescent layer to obtain an aluminum plating base layer; coating a protective layer on the aluminum-plated base layer, printing by a 160-mesh plate roller, and preparing the electrochemical aluminum hot stamping foil with the coating amount of 1.0g per square meter. Through an offset cold stamping test (CY/T194-2019 cold stamping process control requirement and inspection method), the data indexes of the stripping value and the adhesion (13 degrees +0.5s hot stamping on a white card) detection items are obtained, and are shown in tables 1-2:
TABLE 1
Note: * Represents a P <0.05 compared to example 1.
TABLE 2
Note: * Represents a P <0.05 compared to example 1.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The electrochemical aluminum laser layer coating is characterized by comprising the following components in parts by weight: 10-30 parts of isobutyl polymethacrylate resin, 10-30 parts of styrene-indene resin, 40-60 parts of solvent, 3-5 parts of cellulose nitrate and 2-8 parts of locust bean gum.
2. The alumite laser layer coating of claim 1, wherein the styrene-indene resin is prepared by the following method:
(1) According to the weight parts, 10-20 parts of styrene and 5-15 parts of indene are taken, and are stirred and mixed uniformly to obtain a raw material mixed solution;
(2) Adding a catalyst into the raw material mixed solution, heating to 100-150 ℃, and reacting for 20-40min to obtain a polymerization solution;
(3) And (3) removing the catalyst in the polymerization liquid obtained in the step (2), and carrying out reduced pressure distillation on the polymerization liquid with the catalyst removed to obtain the styrene-indene resin.
3. The alumite laser layer coating as claimed in claim 2, wherein the catalyst is sulfuric acid and/or phosphoric acid.
4. The laser coating of electrochemical aluminum according to claim 2, wherein the mass of the catalyst is 1-5% of the raw material mixture.
5. The alumite laser layer coating as claimed in claim 2, wherein the mass ratio of styrene to indene is 1: (0.2-1).
6. The laser electrochemical aluminum layer coating of claim 2, wherein the catalyst removal method comprises: adding calcium hydroxide into the polymerization solution, stirring for 30-60min until the pH of the material is 6.5-8.5, and filtering.
7. The laser coating of the electrochemical aluminum according to claim 2, wherein the reduced pressure distillation method comprises: and carrying out reduced pressure distillation on the polymerization solution from which the catalyst is removed under the conditions of vacuum degree of-0.05 to-0.10 MPa and temperature of 180-220 ℃ until unreacted raw materials are removed, and cooling to room temperature to obtain the styrene-indene resin.
8. The alumite laser layer coating as claimed in claim 1, wherein the solvent is one or more of ethanol, butanone, propanol, n-butanol, ethyl acetate and n-propyl acetate.
9. The method for preparing the coating of the electrochemical aluminum laser layer of claim 1, wherein the isobutyl polymethacrylate resin, the styrene-indene resin, the cellulose nitrate and the locust bean gum are dissolved in the solvent and stirred at a stirring speed of 500-1500m/min for 1-4h.
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| CN105086727A (en) * | 2015-07-31 | 2015-11-25 | 上海维凯光电新材料有限公司 | Laser aluminizing transferring coating high in aluminum-layer adhesion and stripping performance |
| CN106947023A (en) * | 2017-03-10 | 2017-07-14 | 江苏华达化工集团有限公司 | The preparation method of low temperature flow state styrene indene resin |
| CN110654154A (en) * | 2019-09-23 | 2020-01-07 | 刘静 | Positioning gold stamping method for digital thermal transfer printing fabric |
| CN110735339A (en) * | 2019-09-23 | 2020-01-31 | 刘静 | Positioning gold stamping method for wet transfer printing fabrics |
| CN114539867A (en) * | 2022-03-21 | 2022-05-27 | 江苏卫星新材料股份有限公司 | Laser alumite coating and preparation method thereof |
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| CN102643585A (en) * | 2012-04-18 | 2012-08-22 | 上海维凯化学品有限公司 | Laser electrolytic aluminum coating composition and preparation method thereof |
| CN104449541A (en) * | 2013-09-25 | 2015-03-25 | 奇美实业股份有限公司 | Photocurable releasable adhesive composition and use thereof |
| CN105086727A (en) * | 2015-07-31 | 2015-11-25 | 上海维凯光电新材料有限公司 | Laser aluminizing transferring coating high in aluminum-layer adhesion and stripping performance |
| CN106947023A (en) * | 2017-03-10 | 2017-07-14 | 江苏华达化工集团有限公司 | The preparation method of low temperature flow state styrene indene resin |
| CN110654154A (en) * | 2019-09-23 | 2020-01-07 | 刘静 | Positioning gold stamping method for digital thermal transfer printing fabric |
| CN110735339A (en) * | 2019-09-23 | 2020-01-31 | 刘静 | Positioning gold stamping method for wet transfer printing fabrics |
| CN114539867A (en) * | 2022-03-21 | 2022-05-27 | 江苏卫星新材料股份有限公司 | Laser alumite coating and preparation method thereof |
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