CN102351979A - Acrylic resin coating liquid for alumite coloring layer and preparation method thereof - Google Patents
Acrylic resin coating liquid for alumite coloring layer and preparation method thereof Download PDFInfo
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- CN102351979A CN102351979A CN2011102025940A CN201110202594A CN102351979A CN 102351979 A CN102351979 A CN 102351979A CN 2011102025940 A CN2011102025940 A CN 2011102025940A CN 201110202594 A CN201110202594 A CN 201110202594A CN 102351979 A CN102351979 A CN 102351979A
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Abstract
The invention relates to acrylic resin coating liquid for an alumite coloring layer, a preparation method of the acrylic resin coating liquid, the alumite coloring layer prepared from the acrylic resin coating liquid and alumite comprising the coloring layer. The coloring layer has good attaching force to an aluminum plating layer, in addition, the splitting performance is good, and the tightness is proper.
Description
Technical field
The present invention relates to acrylic resin coating fluid of a kind of pigmented layer that is used for electrochemical aluminium and preparation method thereof, and by the pigmented layer that is used for electrochemical aluminium of said acrylic resin coating fluid preparation and the electrochemical aluminium that comprises this pigmented layer.
Background technology
Electrification aluminium is a kind of thermoprint matrix material, comprises base membrane layer, abscission layer, pigmented layer, aluminium coated and adhesive layer.Its preparation method is included in coating abscission layer and pigmented layer on the base membrane layer, through the vacuum aluminum-coated aluminium coated that obtains, and then the coating adhesive layer.Wherein pigmented layer has the effect of protecting aluminium coated, giving color and improve the weather resistance and the weathering resistance of electrochemical aluminium.
At present, because of the singularity of electrochemical aluminium, its relevant report is few.Especially with electrochemical aluminium with the relevant report of pigmented layer still less.And in electrochemical aluminium product, the sticking power of pigmented layer, cutting property and elasticity are normally conflicting technically, are difficult to make these three technical parameters to remain on reasonable range.
Summary of the invention
In order to overcome the problems referred to above, remedy the blank on the prior art, the purpose of this invention is to provide acrylic resin coating fluid of a kind of pigmented layer that is used for electrochemical aluminium and preparation method thereof.
The present invention also aims to provide a kind of by the pigmented layer that is used for electrochemical aluminium of said acrylic resin coating fluid preparation and the electrochemical aluminium that comprises this pigmented layer.
Acrylic resin coating fluid of the present invention can be prepared by the method that may further comprise the steps:
1) solvent adds step, wherein said solvent is joined in the reaction kettle, and is heated to 100～150 ℃;
2) first raw material adds step; Wherein the mixture with first part's initiator, first part's vinyl monomer composition, first part's acrylate monomer compositions and first part's (methyl) acrylate functional monomer composition and said solvent is added drop-wise in the said reaction kettle, and the indirect heating temperature is controlled to be 120～130 ℃;
3) the first insulation reaction step wherein makes to be reflected at 110～130 ℃ and to carry out;
4) second raw material adds step; Wherein the mixture with initiator, second section vinyl monomer composition, second section acrylate monomer compositions and second section (methyl) acrylate functional monomer composition and said solvent is added drop-wise in the said reaction kettle, and the indirect heating temperature is controlled to be 110～120 ℃;
5) the second insulation reaction step wherein makes to be reflected at 110～130 ℃ and to carry out,
The total amount of wherein said (methyl) acrylate monomer compositions is 10～80 weight parts, preferred 30～60 weight parts; The total amount of said (methyl) acrylate functional monomer composition is 1～50 weight part, preferred 5～20 weight parts, and the total amount of said vinyl monomer composition is 1～50 weight part, preferred 10～30 weight parts.
Ratio between the total amount of the total amount of (methyl) acrylate monomer compositions, (methyl) acrylate functional monomer composition, the total amount of vinyl monomer composition can suitably be confirmed as required; As long as can realize technique effect of the present invention, then do not do special qualification.The preferred total amount of (methyl) acrylate monomer compositions: the total amount of (methyl) acrylate functional monomer composition: the ratio of the total amount of vinyl monomer composition is 3～10: 1: 1～6.
In aforesaid method, the weight ratio of first raw material and second raw material and first part's initiator and second section initiator can suitably be selected as required, does not do special qualification.The weight ratio of preferred said first acrylate monomer compositions and said second portion acrylate monomer compositions is 1: 3～3: 1; Be preferably 2: 1～1: 2; More preferably 1: 1; And the weight ratio of said first (methyl) acrylate functional monomer composition and said second portion (methyl) acrylate functional monomer composition is 1: 3～3: 1; Be preferably 2: 1～1: 2; More preferably 1: 1; The weight ratio of said first vinyl monomer composition and said second portion vinyl monomer composition is 1: 3～3: 1; Be preferably 2: 1～1: 2; More preferably 1: 1; The weight ratio of said first initator and said second portion initator is 1: 3～3: 1; Be preferably 2: 1～1: 2, more preferably 1: 1.
Wherein, preferred (methyl) acrylate monomer compositions is 30～60 weight parts, and (methyl) acrylate functional monomer composition is 5～20 weight parts, and the vinyl monomer composition is 10～30 weight parts.It is (methyl) acrylate monomer 5～50 weight parts of 40～80 ℃ that (methyl) acrylate monomer compositions can comprise Tg, and Tg is (methyl) acrylate monomer 5～30 weight parts of-60～20 ℃.In above-mentioned (methyl) acrylate monomer compositions, preferred Tg is that (methyl) acrylate monomer of 40～80 ℃ is 20～40 weight parts, and Tg is 10～20 weight parts for (methyl) acrylate monomer of-60～20 ℃.If wherein Tg is that (methyl) acrylate monomer content of 40～80 ℃ surpasses 50 weight parts, then electrochemical aluminium is pine too, scumming, blind word, stain limit may occur.If be lower than 5 weight parts, its electrochemical aluminium coloring layer maybe be too soft, and cutting property is poor.Surpass 30 weight parts if Tg is (methyl) acrylate monomer of-60～20 ℃, then its pigmented layer maybe be too soft, and cutting property is poor.If be lower than 5 weight parts, then electrochemical aluminium is pine too, scumming, blind word, stain limit occur.Above-mentioned Tg is that (methyl) acrylate monomer of 40～80 ℃ can be at least a in tert-butyl acrylate, cyclohexyl methacrylate, Jia Jibingxisuanyizhi, the n-BMA.Above-mentioned Tg can be at least a in methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, n-butyl acrylate, isobutyl acrylate, the 2-methyl-2-tridecyl acrylate for (methyl) acrylate monomer of-60～20 ℃.
(methyl) acrylate functional monomer composition can comprise (methyl) Acrylic Acid Monomer 0.5～30 weight part with hydroxyl and (methyl) Acrylic Acid Monomer 0.1～30 weight part with carboxyl.In above-mentioned (methyl) acrylate functional monomer composition, (methyl) Acrylic Acid Monomer that preferably has hydroxyl is 2～15 weight parts, and (methyl) Acrylic Acid Monomer with carboxyl is 2～15 weight parts.Wherein, surpass 30 weight parts if having (methyl) Acrylic Acid Monomer of hydroxyl, then electrochemical aluminium may be too tight, and thermoprint is incomplete.Be lower than 0.5 weight part if having (methyl) Acrylic Acid Monomer of hydroxyl, then the fastness difference and the pigment-dispersing ability of pigmented layer and aluminium coated are poor.Wherein, surpass 30 weight parts if having (methyl) Acrylic Acid Monomer of carboxyl, then electrochemical aluminium may be too tight, and thermoprint is incomplete.Be lower than 0.1 weight part if having (methyl) Acrylic Acid Monomer of carboxyl, then the fastness of pigmented layer and aluminium coated is poor.Above-mentioned (methyl) Acrylic Acid Monomer with hydroxyl can be in (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate at least a.Above-mentioned (methyl) Acrylic Acid Monomer with carboxyl can be (methyl) vinylformic acid.
The vinyl monomer composition can comprise vinylbenzene, vinyl acetate and the N-V-Pyrol RC that is respectively 0.1～20 weight part.In the vinyl monomer composition, optimization styrene, vinyl acetate and N-V-Pyrol RC are respectively 2～15 weight parts.Wherein, if styrene content surpasses 20 weight parts, then electrochemical aluminium is pine too, scumming, blind word, stain limit occur.If styrene content is less than 0.1 weight part, then pigmented layer maybe be too soft, and cutting property is poor.If vinyl acetate content surpasses 20 weight parts, then electrochemical aluminium is pine too, scumming, blind word, stain limit occur.If vinyl acetate content is less than 0.1 weight part, then the fastness of pigmented layer and aluminium coated is poor.If the content of N-V-Pyrol RC surpasses 20 weight parts, then electrochemical aluminium may be too tight, and thermoprint is incomplete.If the content of N-V-Pyrol RC is less than 0.1 weight part, then the fastness of pigmented layer and aluminium coated is poor.
In polymerization process, can use initiator.This initiator can be to be selected from least a in tert-butyl peroxide benzoate, di tert butyl carbonate superoxide and the benzoyl peroxide, preferably the composition of at least two kinds of initiators in tert-butyl peroxide benzoate, di tert butyl carbonate superoxide and the benzoyl peroxide.The initiator total amount can be 0.5～2 weight part.More preferably said initiator comprises tert-butyl peroxide benzoate, di tert butyl carbonate superoxide and the benzoyl peroxide that is respectively 0.02～2 weight part.And then more preferably said initiator is the composition of the tert-butyl peroxide benzoate, di tert butyl carbonate superoxide and the benzoyl peroxide that are 0.1～1 weight part.
In above each step; Said solvent is that boiling point is higher than 100 ℃ solvent; Preferred said solvent is the mixed solvent that is higher than 100 ℃ solvent composition by at least two kinds of boiling points, more preferably is selected from the mixed solvent of at least two kinds of solvents in N-BUTYL ACETATE, toluene, xylenes, propyl carbinol, the ethylene glycol ether acetate.The amount of employed solvent can suitably be selected as required in each step.For example the solvent total amount can be 40～80 weight parts.Through using boiling point is the solvent more than 100 ℃, can be so that the molecular weight distribution of acrylic resin is narrower.In addition, in the method for the invention, use mixed solvent, add raw material and to make the purpose of reaction proceed step by step be to prevent that localized heat release from causing the phenomenon of implode to take place, and is easy to the controlled polymerization reaction at twice.
Time to above each step is not done special qualification, and for example first raw material adds step and second raw material interpolation step can be respectively 1～3 hour, is preferably 2 hours; The first insulation reaction step can be 1～3 hour, is preferably 2 hours; The second insulation reaction step can be 1～5 hour, is preferably 3 hours.Insulation reaction finishes, and can obtain containing the reaction product of the acrylic resin of the pigmented layer that is used for electrochemical aluminium of the present invention.The product that contains acrylic resin that above-mentioned reaction can be obtained directly is used as coating fluid, and need not to separate.The solid content of preferred this coating fluid is 55～70 weight %, and viscosity is 1000～3000cps.This coating fluid is coated on the abscission layer of electrochemical aluminium, can obtains pigmented layer after the drying.The sticking power of resulting pigmented layer and aluminium coated is good, and cutting property is good, and elasticity is suitable.
Therefore, the present invention also provides the acrylic resin coating fluid by the pigmented layer that is used for electrochemical aluminium of above method preparation.In addition, the present invention also provides the pigmented layer that is used for electrochemical aluminium that uses acrylic resin coating fluid preparation of the present invention, and the electrochemical aluminium that comprises said pigmented layer.
Embodiment
Understand for technical characterictic of the present invention, purpose and beneficial effect being had more clearly, technical scheme of the present invention is carried out following detailed description, but but can not be interpreted as that following explanation is the qualification to practical range of the present invention at present.
Embodiment 1
Present embodiment provides acrylic resin of a kind of pigmented layer that is used for electrochemical aluminium and preparation method thereof.Wherein, raw material is formed as shown in table 1.The unit of each component is kg in the table, down together.
Table 1
Acrylate composition: acrylate functional monomer composition: vinyl monomer composition=45: 8: 22 ≈ 6: 1: 3
The preparation method of the acrylic resin of present embodiment provides a kind of pigmented layer that is used for electrochemical aluminium is following:
1) N-BUTYL ACETATE 20kg and xylenes 15kg are put into reaction kettle, heating is heated to 120 ℃.
2) with tert-butyl acrylate 15kg, n-butyl acrylate 7.5kg, Rocryl 400 2.5kg; Vinylformic acid 1.5kg; Vinylbenzene 5kg, vinyl acetate 4kg, N-V-Pyrol RC 2kg; Tert-butyl peroxide benzoate 0.25kg; Di tert butyl carbonate superoxide 0.1kg, benzoyl peroxide 0.25kg, N-BUTYL ACETATE 10kg; Xylenes 7.5kg stirs, and drips in 2 hours.During dropping, the externally heating temperature is controlled at 120 ℃.
3) drip to finish after, 120 ℃ of insulation reaction 2 hours.
4) after insulation reaction finishes, remaining tert-butyl acrylate 15kg, n-butyl acrylate 7.5kg; Rocryl 400 2.5kg, vinylformic acid 1.5kg, vinylbenzene 5kg; Vinyl acetate 4kg; N-V-Pyrol RC 2kg, tert-butyl peroxide benzoate 0.25kg, di tert butyl carbonate superoxide 0.1kg; Benzoyl peroxide 0.25kg; N-BUTYL ACETATE 10kg, xylenes 7.5kg stirs, and drips in 2 hours.During dropping, the externally heating temperature is controlled at 115 ℃.
5) drip after, 115 ℃ of insulation reaction 3 hours.
Resulting acrylic resin coating fluid is water white, and wherein the weight-average molecular weight of acrylic resin is 2000, and molecular weight distribution Mn/Mw is 2.1.
Embodiment 2:
Except that the raw material composition is as shown in table 2, according to obtaining acrylic resin of the present invention with embodiment 1 identical mode.Resulting acrylic resin coating fluid is water white, and wherein the weight-average molecular weight of acrylic resin is 1800, and molecular weight distribution Mn/Mw is 1.8.
Table 2
Acrylate composition: acrylate functional monomer composition: vinyl monomer composition=48: 8: 16=6: 1: 2
Embodiment 3:
Except that the raw material composition is as shown in table 3, according to obtaining acrylic resin of the present invention with embodiment 1 identical mode.Resulting acrylic resin coating fluid is water white, and wherein the weight-average molecular weight of acrylic resin is 2400, and molecular weight distribution Mn/Mw is 2.3.
Table 3
Acrylate composition: acrylate functional monomer composition: vinyl monomer composition=50: 6: 22 ≈ 8: 1: 4
Embodiment 4
Except that the raw material composition is as shown in table 4, according to obtaining acrylic resin of the present invention with embodiment 1 identical mode.Resulting acrylic resin coating fluid is water white, and wherein the weight-average molecular weight of acrylic resin is 2500, and molecular weight distribution Mn/Mw is 1.9.
Table 4
Acrylate composition: acrylate functional monomer composition: vinyl monomer composition=18: 6: 30 ≈ 3: 1: 5
Embodiment 5
Except that the raw material composition is as shown in table 5, according to obtaining acrylic resin of the present invention with embodiment 1 identical mode.Resulting acrylic resin coating fluid is water white, and wherein the weight-average molecular weight of acrylic resin is 3200, and molecular weight distribution Mn/Mw is 2.3.
Table 5
Acrylate composition: acrylate functional monomer composition: vinyl monomer composition=40: 10: 12 ≈ 4: 1: 1.2
Comparative example 1:
Comparative example 1 illustrated in the acrylic resin coating fluid, and the selection of various monomeric content is to the influence of the acrylic resin of the chromatograph that is used for electrochemical aluminium.Wherein, raw material is formed as shown in table 6:
Table 6
Acrylate composition: acrylate functional monomer composition: vinyl monomer composition=17: 8: 22 ≈ 2.1: 1: 3
In comparative example 1, the acrylic resin coating fluid that is used for the pigmented layer of electrochemical aluminium prepares with embodiment 1 identical method according to basic.
Comparative example 2:
Comparative example 2 illustrated in the acrylate functional monomer composition, and the selection of monomer content is to the influence of the acrylic resin coating fluid of the chromatograph that is used for electrochemical aluminium.Wherein, raw material is formed as shown in table 7:
Table 7
Acrylate composition: acrylate functional monomer composition: vinyl monomer composition=48: 36: 16 ≈ 1.3: 1: 0.44
In comparative example 2, the acrylic resin coating fluid that is used for the pigmented layer of electrochemical aluminium prepares with embodiment 2 identical methods according to basic.
Test case
Adopt following method to by embodiment 1-5, the performance of the pigmented layer that the acrylic resin coating fluid of the pigmented layer that is used for electrochemical aluminium that comparative example 1-2 provides obtains is estimated.All tests all are on the PET film of parting agent processing, are coated with pigmented layer above it, through 170 ℃ of oven for drying, the test of dry back.
The elasticity test of pigmented layer:
Adopt scotch tape used in everyday to be attached to the pigmented layer surface, after having pasted, press the miter angle stripping tape, with electrochemical aluminium industry those of ordinary skill on hand the size of stressing conditions judge the elasticity of pigmented layer.
Sticking power test with aluminium coated:
On the pigmented layer behind the evaporation plating aluminium, use scotch tape to be attached to the aluminium coated surface, after having pasted, peel off rapidly, stay the sticking power with aluminium coated of how much judging of look at the pet sheet face.Judgement criteria is following:
Good: as not have and stay look
Difference: big area is stayed look
Generally: facet accumulates look
Cut the test of performance:
Adopt the pattern mold of different densities to carry out thermoprint.When thermoprint was complete, the size of pattern density was judged its cutting property.Judgement criteria is following:
Good: the pattern thermoprint that density is bigger is clear.
Difference: the pattern thermoprint that density is little is clear, and the pattern thermoprint that density is moderate is unintelligible.
Generally: the pattern thermoprint that density is moderate is clear, and the pattern thermoprint that density is bigger is unintelligible.
Test result is following:
Table 8
Can know that by last table 8 pigmented layer that the coating fluid through the embodiment of the invention 1 to 5 obtains can be so that elasticity, sticking power and cutting property all be in reasonable range.
Claims (11)
1. the preparation method of the acrylic resin coating fluid of a pigmented layer that is used for electrochemical aluminium is characterized in that, said method comprising the steps of:
1) solvent adds step, wherein said solvent is joined in the reaction kettle, and is heated to 100～150 ℃;
2) first raw material adds step; Wherein the mixture with first part's initiator, first part's vinyl monomer composition, first part's acrylate monomer compositions and first part's (methyl) acrylate functional monomer composition and said solvent is added drop-wise in the said reaction kettle, and the indirect heating temperature is controlled to be 120～130 ℃;
3) the first insulation reaction step wherein makes to be reflected at 110～130 ℃ and to carry out;
4) second raw material adds step; Wherein the mixture with second section initiator, second section vinyl monomer composition, second section acrylate monomer compositions and second section (methyl) acrylate functional monomer composition and said solvent is added drop-wise in the said reaction kettle, and the indirect heating temperature is controlled to be 110～120 ℃;
5) the second insulation reaction step wherein makes to be reflected at 110～130 ℃ and to carry out,
The total amount of wherein said (methyl) acrylate monomer compositions is 10～80 weight parts, preferred 30～60 weight parts; The total amount of said (methyl) acrylate functional monomer composition is 1～50 weight part, preferred 5～20 weight parts, and the total amount of said vinyl monomer composition is 1～50 weight part, preferred 10～30 weight parts.
2. preparation method as claimed in claim 1; It is characterized in that; The weight ratio of said first acrylate monomer compositions and said second portion acrylate monomer compositions is 1: 3～3: 1; Be preferably 2: 1～1: 2; More preferably 1: 1; And the weight ratio of said first (methyl) acrylate functional monomer composition and said second portion (methyl) acrylate functional monomer composition is 1: 3～3: 1; Be preferably 2: 1～1: 2; More preferably 1: 1; The weight ratio of said first vinyl monomer composition and said second portion vinyl monomer composition is 1: 3～3: 1; Be preferably 2: 1～1: 2; More preferably 1: 1; The weight ratio of said first initator and said second portion initator is 1: 3～3: 1; Be preferably 2: 1～1: 2; More preferably 1: 1, the total amount of preferred (methyl) acrylate monomer compositions: the total amount of (methyl) acrylate functional monomer composition: the ratio of the total amount of vinyl monomer composition was 3～10: 1: 1～6.
3. preparation method as claimed in claim 1 or 2; It is characterized in that the Tg that said (methyl) acrylate monomer compositions comprises 5～50 weight parts, preferred 20～40 weight parts is that the Tg of 40～80 ℃ (methyl) acrylate monomer and 5～30 weight parts, preferred 10～20 weight parts is (methyl) acrylate monomer of-60～20 ℃.
4. preparation method as claimed in claim 3; It is characterized in that; Said Tg is that (methyl) acrylate monomer of 40～80 ℃ is to be selected from least a in tert-butyl acrylate, cyclohexyl methacrylate, Jia Jibingxisuanyizhi and the n-BMA, and said Tg is to be selected from least a in methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, n-butyl acrylate, isobutyl acrylate and the 2-methyl-2-tridecyl acrylate for (methyl) acrylate monomer of-60～20 ℃.
5. preparation method as claimed in claim 1 or 2; It is characterized in that said (methyl) acrylate functional monomer composition comprises (methyl) Acrylic Acid Monomer with hydroxyl and 0.1～30 weight part of 0.5～30 weight part, preferred 2～15 weight parts, (methyl) Acrylic Acid Monomer with carboxyl of preferred 2～15 weight parts.
6. preparation method as claimed in claim 5; It is characterized in that; Said (methyl) Acrylic Acid Monomer with hydroxyl is to be selected from least a in (methyl) Hydroxyethyl acrylate and (methyl) Propylene glycol monoacrylate, and said (methyl) Acrylic Acid Monomer with carboxyl is (methyl) vinylformic acid.
7. preparation method as claimed in claim 1 or 2; It is characterized in that; Said vinyl monomer composition comprises the vinylbenzene of 0.1～20 weight part, preferred 2～15 weight parts, the N-V-Pyrol RC of the vinyl acetate of 0.1～20 weight part, preferred 2～15 weight parts and 0.1～20 weight part, preferred 2～15 weight parts.
8. preparation method as claimed in claim 1 or 2; It is characterized in that; Said initiator is to be selected from tert-butyl peroxide benzoate; At least a in di tert butyl carbonate superoxide and the benzoyl peroxide; The tert-butyl peroxide benzoate of 0.02～2 weight part preferably; 0.02 the composition of the di tert butyl carbonate superoxide of～2 weight parts and the benzoyl peroxide of 0.02～2 weight part is more preferably the tert-butyl peroxide benzoate of 0.1～1 weight part; 0.1 the composition of the di tert butyl carbonate superoxide of～1 weight part and the benzoyl peroxide of 0.1～1 weight part.
9. preparation method as claimed in claim 1 or 2; It is characterized in that; Said solvent is that boiling point is higher than 100 ℃ solvent; Preferred said solvent is the mixed solvent by at least two kinds of solvent compositions, more preferably by the mixed solvent that is selected from least two kinds of solvent compositions in N-BUTYL ACETATE, toluene, xylenes, propyl carbinol, the ethylene glycol ether acetate.
10. acrylic resin coating fluid that is used for the pigmented layer of electrochemical aluminium, said coating fluid through as in the claim 1 to 9 each described preparation method prepare.
11. a pigmented layer that is used for electrochemical aluminium, the said pigmented layer that is used for electrochemical aluminium is prepared by acrylic resin coating fluid as claimed in claim 10.
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| CN104017318A (en) * | 2014-05-13 | 2014-09-03 | 佛山市南海高拓包装材料有限公司 | Information level resin for alumite and preparation method of alumite as well as alumite stamping foil |
| CN104531009A (en) * | 2014-12-31 | 2015-04-22 | 东莞光群雷射科技有限公司 | Offset print cold stamping dual-purpose adhesive and preparation method and usage method thereof |
| CN105694561A (en) * | 2016-03-15 | 2016-06-22 | 扬州市祥华新材料科技有限公司 | Alumite color layer coating containing acrylic monomers |
| CN107629603A (en) * | 2017-10-19 | 2018-01-26 | 武汉华工图像技术开发有限公司 | Wear-resisting chromatograph coating and the wear-resisting chromatograph of formation, wear-resisting anodized aluminium and preparation method thereof |
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| CN109651559B (en) * | 2018-12-11 | 2021-11-09 | 上海绘兰材料科技有限公司 | Acrylic resin for release-free ironing cloth electrochemical aluminum and preparation method and application thereof |
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| CN112322086A (en) * | 2020-10-09 | 2021-02-05 | 武汉华中科大新材料股份有限公司 | Electrochemical aluminum coating and preparation method thereof |
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| CN112322092A (en) * | 2020-11-25 | 2021-02-05 | 云南玉溪东魅包装材料有限公司 | Alumite coloring layer coating with high wrapping capacity and preparation method thereof |
| CN112497946A (en) * | 2020-11-26 | 2021-03-16 | 武汉华工图像技术开发有限公司 | Electrochemical aluminum foil and preparation method thereof |
| CN112497946B (en) * | 2020-11-26 | 2022-07-29 | 武汉华工图像技术开发有限公司 | Electrochemical aluminum foil and preparation method thereof |
| CN112592634A (en) * | 2020-12-16 | 2021-04-02 | 广东镭宝光电科技有限公司 | Laser layer coating for improving information reproduction of alumite and preparation method thereof |
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