CN102417796A - Metal decorating film with hardened protective layer and preparation method thereof - Google Patents
Metal decorating film with hardened protective layer and preparation method thereof Download PDFInfo
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- CN102417796A CN102417796A CN2011102534387A CN201110253438A CN102417796A CN 102417796 A CN102417796 A CN 102417796A CN 2011102534387 A CN2011102534387 A CN 2011102534387A CN 201110253438 A CN201110253438 A CN 201110253438A CN 102417796 A CN102417796 A CN 102417796A
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Abstract
The invention discloses a metal decorating film with a hardened protective layer and a preparation method thereof. The metal decorating film comprises a support body, a stripping layer, a decorating layer and a sticking layer. After improvements, the stripping layer and the decorating layer are coated with the hardened protective layer. The hardened protective layer comprises the following components in part by weight: 20-50 parts of multifunctional acrylic resin prepolymer, 15-25 parts of styrene-maleic anhydride copolymer resin, 0-10 parts of active diluent, 2-5 parts of photo initiator, 0.02-0.1 parts of flatting agent and 30-60 parts of solvent, wherein the solvent consists of a high-boiling-point solvent and a low-boiling-point solvent in the weight ratio of 1:5-1:2. The decorating film has the advantages of plump effect, glossiness of over 800 Gs, high heat resistance, high wear resistance, high chemical resistance performance, high coating adhesion and strong drawing force.
Description
Technical field
The present invention relates to a kind of decorative metal film, particularly a kind of decorative metal film that has the resist that hardens.
Background technology
Along with the development of society, products such as household electrical appliance, automobile, mobile phone have all adopted plastic component in a large number, and it requires increasingly highly to surface decoration, as requires plastic component to have the mirror metal makeup decorations effect etc. of high gloss.
In the past, the mirror metal makeup decorations of metallization, the especially high gloss on these plastic component surfaces, its technology is to adopt technologies such as plating, thermoprint mostly.Liquid method electroplating technology has bigger pollution because of existing to environment, and it is used gradually and reduces; Vacuum plating process because of its to the having relatively high expectations of plastic component, need before plating, add stopping off after precoating bottom, the plating, cause cost to increase, and this technology is decorated difficult the realization to the metallization of plastic component.
Thermoprint is a dry process, has the characteristics of environmental protection, thereby receives an acclaim gradually.Hot stamping process has been widely applied to the metallization decoration of various plastic component at present.The decorative metal film of frosting thermoprint, its structure comprises tape base, peel ply, resist, metal level, adhered layer.Through the thermoprint process, be the metallic mirror surface effect though can frosting be decorated, there is following shortcoming in it: hardness is generally less than HB, and solvent resistance and wear resisting property are poor.
For addressing the above problem, take to increase resist, vacuum evaporation or sputter hardened layer in the prior art usually, still, increase resist and need use coatings volatile organic compounds and increase production process, cause environmental pollution like this and increased production cost; If vacuum evaporation or sputter hardened layer, then since hardening coat to the repulsion of vacuum evaporation or sputter, to cause behind the plated film interlayer of product to adhere to relatively poor, coat of metal is prone to come off after the thermoprint, influences the decorative effect of plastic component.
Summary of the invention
The technical problem that the present invention will solve provides a kind of decorative metal film that has the resist that hardens.
Another technical problem that the present invention will solve provides this preparation method who has the decorative metal film of the resist that hardens.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is:
A kind of decorative metal film that has the resist that hardens, it comprises support, peel ply, ornament layer and adhered layer, is coated with the sclerosis resist at peel ply and ornament layer, the component of said sclerosis resist and weight part thereof are:
20～50 parts of polyfunctionality vinyl resin prepolymers;
15～25 parts of phenylethylene-maleic anhydride copolymer resinses;
0～10 part of reactive thinner;
2～5 parts of light triggers;
0.02～0.1 part of flow agent;
30～60 parts of solvents;
Said solvent is made up of high boiling solvent and low boiling point solvent, and the weight ratio between high boiling solvent and the low boiling point solvent is between 1:5 to 1:2.
Said polyfunctionality vinyl resin prepolymer is that functionality is not less than 3 acroleic acid resin prepolymer.
Said phenylethylene-maleic anhydride copolymer resins be molecular weight between 1000～20000, acid number is greater than 200, the Tg value is greater than 120 ℃ phenylethylene-maleic anhydride copolymer resins.
Said reactive thinner is an ethoxylated trimethylolpropane triacrylate.
Said high boiling solvent is an isobutyl acetate, and said low boiling point solvent is the mixed solvent of butanone and ETHYLE ACETATE.
The thickness of said sclerosis resist is 1～5 micron.
Another object of the present invention is achieved in that
A kind ofly prepare the above-mentioned method that has the decorative metal film of the resist that hardens, it carries out as follows:
⑴. on support, be coated with peel ply;
⑵. the above-mentioned sclerosis resist of coating on peel ply;
⑶. vacuum plating on the sclerosis resist;
⑷. the coating adhered layer obtains having the decorative metal film of resist of hardening.
Compared with prior art, the present invention has following advantage:
⑴. this decorative metal film contains the sclerosis resist, and thermoprint is behind the plastic component surface, and not needing increases resist again, has reduced production cost of products, has avoided the environmental pollution because of adopting coatings volatile organic compounds to cause.
⑵. the sclerosis resist surfacing of adopting coating method to obtain, metal effect is plentiful behind the plated film, and glossiness reaches more than the 800Gs.
⑶. after this decorative metal film is applied to the plastic component surface, have good heat-resisting, wear-resisting, chemical resistance, excellent plated film tack and force-to-stretch.Its adhesion property of cross-hatching test is good, and ethanol-tolerant and anti-butanone wiping number of times be more than 100 times, surface hardness 1H-2H, and anti-paper tape abrasion are more than 20 times, and force-to-stretch is between 5-30%.
⑷. coating curing speed is fast, can reach 20-150m/min, solidifies the back resistance toheat and reaches more than 180 ℃.
Embodiment
The effect of polyfunctionality vinyl resin prepolymer provides the matrix resin and the reflecting point of coating curing among the present invention, forms through light initiation polymerization to have cancellated coating, realize high temperature resistant, wear-resisting and solvent-proof performance.If the functionality of resin is low then reflecting point is limited, the coating curing degree can not satisfy performance requriements.Be fit to polyfunctionality vinyl resin prepolymer of the present invention and include but not limited to following resin: trihydroxy-triacrylate prepolymer, trihydroxy-tetraacrylate prepolymer, two trihydroxy-propane tetraacrylate prepolymer, pentaerythritol triacrylate prepolymer, NSC 65881 triacrylate prepolymer etc.
The effect of phenylethylene-maleic anhydride copolymer resins provides the plated film adhesion property and the fullness ratio of coating, and subparticipation reaction, reduces the shrinking percentage of coating, under the coating condition, has good apparent.Said phenylethylene-maleic anhydride copolymer resins is that molecular weight is between 1000-20000; Acid number is greater than 200; The Tg value is fit to phenylethylene-maleic anhydride resin of the present invention and includes but not limited to following product: the SMA1000 of Sartomer company, SMA2000, SMA3000 series etc. greater than 120 ℃ phenylethylene-maleic anhydride copolymer resins.
Said reactive thinner is an ethoxylated trimethylolpropane triacrylate.Ethoxylated trimethylolpropane triacrylate is the trifunctional function monomer.It has the highly active while, can give cured film good snappiness, and the main energy supply in the sclerosis resist is the snappiness of adjustment coating.
Light trigger among the present invention is a free radical photo-initiation, and its major function provides light initiation polymerization fast, has the high characteristics of efficiency of initiation.The present invention can use single-initiator or composite initiator.As: 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio group) phenyl]-1-acetone, 2; 4; 6-trimethylbenzoyl-diphenyl phosphine oxide, 2; 4, one or more in the 6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester etc., the commercial light trigger of using among the present invention comprise 184,1173, among the TPO etc. one or more.
Flow agent among the present invention is polymethyl siloxane or modification methyl polysilicone alkanes material, and like propenoate-ZGK 5 etc., the effect of flow agent mainly provides coating coating and film forming flow leveling, has the effect that increases wear resisting property simultaneously.
Said solvent is made up of high boiling solvent and low boiling point solvent, between the ratio 1:5 to 1:2 between high boiling solvent and the low boiling point solvent.Said high boiling solvent is an isobutyl acetate, and said low boiling point solvent is the mixed solvent of butanone and ETHYLE ACETATE.
The preparation process of the protective layer used coating fluid of said sclerosis is following:
⑴. quantitative butanone is added in the reaction vessel, add the phenylethylene-maleic anhydride resin, be stirred to dissolving fully;
⑵. in the stirring, light trigger is joined in the good above-mentioned resin solution of dissolving, and add ETHYLE ACETATE and isobutyl acetate solvent, stir;
⑶. add polyfunctional acrylic ester prepolymer and reactive thinner, stir;
⑷. add flow agent, be stirred to and mix.
The preparation process of the said decorative metal film that has a resist that hardens is following:
⑴. go up the coating peel ply at support (like the PET tape base);
⑵. the above-mentioned sclerosis resist of coating on peel ply;
⑶. vacuum plating on the sclerosis resist;
⑷. the coating adhered layer obtains having the decorative metal film of resist of hardening.
Said coating method adopts coating methods such as the coating of known anilox roll, the coating of nick version, the coating of silk rod, intaglio plate coating, the resist that hardens thickness be the 1-5 micron.
After the said decorative metal film that has the resist that hardens is used processing, break away between sclerosis resist and the peel ply, peel ply and support are stripped from together, and decorated surface is the sclerosis resist.
Below in conjunction with embodiment the present invention is further specified, but the present invention is not limited to this.
Embodiment 1
1. the harden preparation of protective layer used coating fluid:
50.0 parts of trihydroxy-propane tetraacrylate prepolymers,
15.0 parts of phenylethylene-maleic anhydride resins,
184 1.0 parts,
0.45 part of TPO,
0.05 part of YSR 3286,
10.0 parts in ETHYLE ACETATE,
15.0 parts of butanone,
8.5 parts of isobutyl acetates,
1. butanone is added in the reaction vessel, add the phenylethylene-maleic anhydride resin, stir 30min, dissolving fully; 2. in stirring, light trigger 184 is joined in the good resin solution of dissolving with TPO, and add ETHYLE ACETATE and isobutyl acetate solvent, stir 10-20min, mix; 3. add trihydroxy-propane tetraacrylate prepolymer, and stir 30min; 4. add the flow agent YSR 3286, be stirred to and mix, protective layer used coating fluid obtains hardening.
2. the preparation of decorative metal film:
Adopt anilox roll technology above-mentioned sclerosis protective layer coating solution to be applied on the PET film support that is coated with peel ply, 2 microns of sclerosis protective layer thickness, plated film, coating adhered layer again after the coating are finished product.To ABS plastic spare, test each item performance is following with the decorative metal film thermoprint that obtains:
The interlayer tack: cross-hatching test adhesion property is good;
Ethanol-tolerant wiping number of times: 300 times;
Surface hardness: 2H;
Anti-paper tape abrasion exist: 25 times;
Snappiness: force-to-stretch 10%.
Embodiment 2
1. the harden preparation of protective layer used coating fluid:
20.0 parts of trihydroxy-propane tetraacrylate prepolymers,
20.0 parts of phenylethylene-maleic anhydride resins,
3.0 parts of ethoxylated trimethylolpropane triacrylates,
1.0 parts of TPO,
365 0.45 parts,
0.05 part of YSR 3286,
20.0 parts in ETHYLE ACETATE,
30.0 parts of butanone,
5.5 parts of isobutyl acetates,
1. butanone is added in the reaction vessel, add the phenylethylene-maleic anhydride resin, stir 30min, dissolving fully; 2. in stirring, light trigger 184 is joined in the good resin solution of dissolving with TPO, and add ETHYLE ACETATE and isobutyl acetate solvent, stir 10-20min, mix; 3. add trihydroxy-propane tetraacrylate prepolymer, and stir 30min; 4. add ethoxylated trimethylolpropane triacrylate, be stirred to evenly;
adds the flow agent YSR 3286; Be stirred to and mix, protective layer used coating fluid obtains hardening.
2. the preparation of decorative metal film:
Adopt the excellent coating process of silk above-mentioned sclerosis protective layer coating solution to be applied on the PET film support that is coated with peel ply, 3.5 microns of sclerosis protective layer thickness, plated film, coating adhered layer again after the coating are finished product.To ABS plastic spare, test each item performance is following with the decorative metal film thermoprint that obtains:
The interlayer tack: cross-hatching test adhesion property is good;
Ethanol-tolerant wiping number of times: 300 times;
Surface hardness: 1H;
Anti-paper tape abrasion exist: 30 times;
Snappiness: force-to-stretch 15%.
Embodiment 3
1. the harden preparation of protective layer used coating fluid:
30.0 parts of trihydroxy-propane tetraacrylate prepolymers,
25.0 parts of phenylethylene-maleic anhydride resins,
6.0 parts of ethoxylated trimethylolpropane triacrylates,
1.0 parts of TPO,
365 0.45 parts,
0.05 part of YSR 3286,
20.0 parts in ETHYLE ACETATE,
32.0 parts of butanone,
5.0 parts of isobutyl acetates,
1. butanone is added in the reaction vessel, add the phenylethylene-maleic anhydride resin, stir 30min, dissolving fully; 2. in stirring, light trigger 184 is joined in the good resin solution of dissolving with TPO, and add ETHYLE ACETATE and isobutyl acetate solvent, stir 10-20min, mix; 3. add trihydroxy-propane tetraacrylate prepolymer, and stir 30min; 4. add ethoxylated trimethylolpropane triacrylate, be stirred to evenly;
adds the flow agent YSR 3286; Be stirred to and mix, protective layer used coating fluid obtains hardening.
2. the preparation of decorative metal film:
Adopt anilox roll technology above-mentioned sclerosis protective layer coating solution to be applied on the PET film support that is coated with peel ply, 1.0 microns of sclerosis protective layer thickness, plated film, coating adhered layer again after the coating are finished product.To ABS plastic spare, test each item performance is following with the decorative metal film thermoprint that obtains:
The interlayer tack: cross-hatching test adhesion property is good;
Ethanol-tolerant wiping number of times: 200 times;
Surface hardness: 1H;
Anti-paper tape abrasion exist: 20 times;
Snappiness: force-to-stretch 25%.
Embodiment 4
1. the harden preparation of protective layer used coating fluid:
40.0 parts of trihydroxy-propane tetraacrylate prepolymers,
15.0 parts of phenylethylene-maleic anhydride resins,
10.0 parts of ethoxylated trimethylolpropane triacrylates,
1.0 parts of TPO,
365 0.45 parts,
0.05 part of YSR 3286,
10.0 parts in ETHYLE ACETATE,
16.0 parts of butanone,
7.5 parts of isobutyl acetates,
1. butanone is added in the reaction vessel, add the phenylethylene-maleic anhydride resin, stir 30min, dissolving fully; 2. in stirring, light trigger 184 is joined in the good resin solution of dissolving with TPO, and add ETHYLE ACETATE and isobutyl acetate solvent, stir 10-20min, mix; 3. add trihydroxy-propane tetraacrylate prepolymer, and stir 30min; 4. add ethoxylated trimethylolpropane triacrylate, be stirred to evenly;
adds the flow agent YSR 3286; Be stirred to and mix, protective layer used coating fluid obtains hardening.
2. the preparation of decorative metal film:
Adopt anilox roll technology above-mentioned sclerosis protective layer coating solution to be applied on the PET film support that is coated with peel ply, 5.0 microns of sclerosis protective layer thickness, plated film, coating adhered layer again after the coating are finished product.To ABS plastic spare, test each item performance is following with the decorative metal film thermoprint that obtains:
The interlayer tack: cross-hatching test adhesion property is good;
Ethanol-tolerant wiping number of times: 400 times;
Surface hardness: 2H;
Anti-paper tape abrasion exist: 45 times;
Snappiness: force-to-stretch 30%.
Claims (7)
1. decorative metal film that has the resist that hardens, it comprises support, peel ply, ornament layer and adhered layer, it is characterized in that, is coated with the sclerosis resist at peel ply and ornament layer, the component of said sclerosis resist and weight part thereof are:
20～50 parts of polyfunctionality vinyl resin prepolymers;
15～25 parts of phenylethylene-maleic anhydride copolymer resinses;
0～10 part of reactive thinner;
2～5 parts of light triggers;
0.02～0.1 part of flow agent;
30～60 parts of solvents;
Said solvent is made up of high boiling solvent and low boiling point solvent, and the weight ratio between high boiling solvent and the low boiling point solvent is between 1:5 to 1:2.
2. decorative metal film according to claim 1 is characterized in that, said polyfunctionality vinyl resin prepolymer is that functionality is not less than 3 acroleic acid resin prepolymer.
3. decorative metal film according to claim 2 is characterized in that, said phenylethylene-maleic anhydride copolymer resins be molecular weight between 1000～20000, acid number greater than 200, the Tg value is greater than 120 ℃ phenylethylene-maleic anhydride copolymer resins.
4. according to the said decorative metal film of claim 3, it is characterized in that said reactive thinner is an ethoxylated trimethylolpropane triacrylate.
5. decorative metal film according to claim 4 is characterized in that, said high boiling solvent is an isobutyl acetate, and said low boiling point solvent is the mixed solvent of butanone and ETHYLE ACETATE.
6. decorative metal film according to claim 5 is characterized in that, the thickness of said sclerosis resist is 1～5 micron.
7. one kind prepares like claim 1,2,3,4, the 5 or 6 described methods that have the decorative metal film of the resist that hardens, and it is characterized in that it carries out as follows:
⑴. on support, be coated with peel ply;
⑵. the above-mentioned sclerosis resist of coating on peel ply;
⑶. vacuum plating on the sclerosis resist;
⑷. the coating adhered layer obtains having the decorative metal film of resist of hardening.
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| CN2011102534387A CN102417796A (en) | 2011-08-31 | 2011-08-31 | Metal decorating film with hardened protective layer and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102642440A (en) * | 2012-05-11 | 2012-08-22 | 保定乐凯新材料股份有限公司 | Double-faced drawing decorative film for transparent plastic component |
| CN103625202A (en) * | 2013-12-13 | 2014-03-12 | 保定乐凯新材料股份有限公司 | Drawing decorative film with frosting effect |
| CN104908380A (en) * | 2015-06-30 | 2015-09-16 | 保定乐凯新材料股份有限公司 | Transfer decoration film |
| CN105713496A (en) * | 2014-12-02 | 2016-06-29 | 合众（佛山）化工有限公司 | Preparation method of aqueous two-component super wear-resistant lusterless paint |
| CN110039836A (en) * | 2018-01-15 | 2019-07-23 | 南昌欧菲光学技术有限公司 | Decorating film |
| CN114181574A (en) * | 2021-12-24 | 2022-03-15 | 上海华工艾马尔新材料有限公司 | Wear-resistant coating, preparation method thereof and decorative film |
| CN115260842A (en) * | 2022-08-08 | 2022-11-01 | 山东东宏管业股份有限公司 | High-adhesion and crack-resistant polyethylene powder and preparation method and application thereof |
| CN116766807A (en) * | 2023-06-25 | 2023-09-19 | 湖南同丰艺达薄膜科技有限公司 | High-resistance decorative film and preparation method thereof |
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| CN102146226A (en) * | 2010-12-28 | 2011-08-10 | 西安航天三沃化学有限公司 | Ultraviolet-cured high-adhesion scraping-resistant agent for heat insulating film |
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| CN101935494A (en) * | 2010-08-18 | 2011-01-05 | 梁鹏飞 | Ultraviolet-cured resin composition and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102642440A (en) * | 2012-05-11 | 2012-08-22 | 保定乐凯新材料股份有限公司 | Double-faced drawing decorative film for transparent plastic component |
| CN102642440B (en) * | 2012-05-11 | 2014-11-12 | 保定乐凯新材料股份有限公司 | Double-faced drawing decorative film for transparent plastic component |
| CN103625202A (en) * | 2013-12-13 | 2014-03-12 | 保定乐凯新材料股份有限公司 | Drawing decorative film with frosting effect |
| CN103625202B (en) * | 2013-12-13 | 2016-09-14 | 保定乐凯新材料股份有限公司 | A kind of wire drawing decorative film with frosted finish effect |
| CN105713496A (en) * | 2014-12-02 | 2016-06-29 | 合众（佛山）化工有限公司 | Preparation method of aqueous two-component super wear-resistant lusterless paint |
| CN104908380A (en) * | 2015-06-30 | 2015-09-16 | 保定乐凯新材料股份有限公司 | Transfer decoration film |
| CN110039836A (en) * | 2018-01-15 | 2019-07-23 | 南昌欧菲光学技术有限公司 | Decorating film |
| CN110039836B (en) * | 2018-01-15 | 2023-12-05 | 安徽精卓光显技术有限责任公司 | decorative film |
| CN114181574A (en) * | 2021-12-24 | 2022-03-15 | 上海华工艾马尔新材料有限公司 | Wear-resistant coating, preparation method thereof and decorative film |
| CN115260842A (en) * | 2022-08-08 | 2022-11-01 | 山东东宏管业股份有限公司 | High-adhesion and crack-resistant polyethylene powder and preparation method and application thereof |
| CN116766807A (en) * | 2023-06-25 | 2023-09-19 | 湖南同丰艺达薄膜科技有限公司 | High-resistance decorative film and preparation method thereof |
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Application publication date: 20120418 |