CN102673287A - Non-halogen transfer type decoration film used for plastic surface decoration - Google Patents
Non-halogen transfer type decoration film used for plastic surface decoration Download PDFInfo
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- CN102673287A CN102673287A CN201210147957XA CN201210147957A CN102673287A CN 102673287 A CN102673287 A CN 102673287A CN 201210147957X A CN201210147957X A CN 201210147957XA CN 201210147957 A CN201210147957 A CN 201210147957A CN 102673287 A CN102673287 A CN 102673287A
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Abstract
The invention discloses a non-halogen transfer type decoration film used for plastic surface decoration, which comprises a supporter, a release layer, a hardened protection layer, a metal decoration layer and a sticking layer, wherein the halogen content in the sticking layer is less than 600ppm; the sticking layer comprises the following components according to parts by weight: 8-16 parts of thermoplastic acrylic resin, 5-10 parts of maleic anhydride copolymer resin, 4-8 parts of polyvinyl butyral, 1-2 parts of isocyanate resin, 2-4 parts of aerosil and 60-80 parts of solvent. The halogen content in the decoration film disclosed by the invention is less than 600ppm so as to satisfy the non-halogen decoration requirement of plastic accessories, such as ABS (Acrylonitrile Butadiene Styrene), PC (Polycarbonate), PMMA (Polymethyl Methacrylate), PS (Polystyrene) and the like. In addition, the non-halogen transfer type decoration film has good adhesion attachment fastness with general plastics, such as the ABS, the PC, the PMMA, the PS and the like, no falling during a tape test and excellent thermoprint definition.
Description
Technical field
The present invention relates to a kind of decorating film, particularly a kind of non-halogen transfer printing type decorating film that is used for the plastic cement incrustation.
Background technology
Along with social development with to the improving constantly of environmental requirement, the working of plastics of part household electrical appliances and 3C Product has adopted the technology of surperficial thermoprint or in-mold transfer printing to carry out the decoration of surface effect, to substitute spraying or electroplating technology.And along with the improving constantly of environmental requirement, the environmental requirement of plastic fittings is also being strengthened, in recent years; Europe has proposed non-halogen requirement; That is: chlorine＜600ppm, fluorine＜600ppm, iodine＜600ppm; Simultaneously, the part plastic fitting processing enterprise of China has also proposed non-halogen requirement to the transfer decorative film that is used for plastic fittings.
In the prior art; The decorating film that is used for the plastic fitting decoration all contains halogen; Especially the content of chlorine element is greater than 600ppm; Halogen mainly is present in the adhered layer of transfer decorative film, and its main cause is usually to use the polymer of chloride elements such as chloridized polyolefin resinoid, vinyl chloride-vinyl acetate resin in the adhered layer.The application of these polymer in adhered layer caused halogen; Especially the content ratio of chlorine element has exceeded non-halogen claimed range; The transfer decorative film content of halogen test that causes making exceeds standard; Do not meet environmental requirement, in actual life, cause environmental pollution easily and endanger the healthy of user.
Summary of the invention
Technical problem to be solved by this invention provides a kind of non-halogen transfer printing type decorating film that is used for the plastic cement incrustation, to improve the environmental-protecting performance of transfer decorative film.
For addressing the above problem, the technical scheme that the present invention adopts is:
A kind of non-halogen transfer printing type decorating film that is used for the plastic cement incrustation, it comprises: support, release layer, sclerosis protective layer, metal finishing layer and adhered layer, the content of halogen in the said adhered layer are less than 600ppm, and component that adhered layer contains and weight portion are:
8～16 parts of thermoplastic acrylic resins;
5～10 parts of maleic anhydride copolymer resinses;
4～8 parts of polyvinyl butyral resins;
1～2 part of isocyanate resin;
2～4 parts of aerosils;
60～80 parts of solvents.
Above-mentioned decorating film, described thermoplastic acrylic resin be molecular weight between 30000～70000, the Tg value is at 45 ℃～70 ℃ the methyl methacrylate and the copolymer of n-BMA.
Above-mentioned decorating film, described maleic anhydride copolymer resins is between 1000～20000, acid number 50～500, the Tg value is at 50 ℃～80 ℃ maleic anhydride copolymer resins.
Above-mentioned decorating film, described solvent are the mixed solvent of butanone, ethyl acetate, its weight ratio 1:1～1:2.
Above-mentioned decorating film, the thickness of said adhered layer are 1～2 micron.
Compared with prior art: the present invention has following advantage:
1. content of halogen＜the 600ppm in the decorating film meets the non-halogen environmental protection application requirements of product.
2. the present invention is through the cooperation between thermoplastic acrylic resin, maleic anhydride copolymer resins and the polyvinyl butyral resin; And through and an amount of isocyanate resin between crosslinked; Formed simultaneously good the adhering to thermoprint of metal finishing layer adhered to the good of surface such as ABS, PMMA, PC, PS; Adhesion effect has reached the effect that adopts chlorinated polyolefin resin or vinyl chloride-vinyl acetate resin, can effectively substitute chlorine-containing resins.
3. decorating film provided by the invention guarantee non-halogen in, good to the thermoprint attachment fastness of general-purpose plastics such as ABS, PC, PMMA, PS under 160-250 ℃ of boiling hot condition, adhesive tape test does not have and comes off, the thermoprint definition is good.
4. decorating film provided by the invention scalds back case hardness height, wear-resisting and chemicals-resistant characteristic good.
The specific embodiment
Thermoplastic acrylic resin described in the present invention is the copolymer of methyl methacrylate and n-BMA; Molecular weight is between 30000-70000; The Tg value is at 45 ℃～70 ℃; This thermoplastic acrylic resin is the basic link stuff of thermoprint gum, can activation under the thermoprint condition between 160-250 ℃, general-purpose plastics base materials such as ABS, PMMA, PC, PS are had good adhesion effect; Simultaneously since the elongation at break of thermoplastic acrylic resin about 5%, the thermoprint lines or the literal that help the transfer decorative film are clear.Acrylic resin in being suitable for inventing includes but not limited to: the LP65/11 of Degussa, LP64/12 etc.
Maleic anhydride copolymer resins described in the present invention is between the 1000-20000, acid number 50-500, the maleic anhydride copolymer resins of Tg value between 50-80 ℃.The function of maleic anhydride copolymer resins provides a large amount of carboxyls, improves the adhesion effect of adhered layer to the metal finishing layer, satisfies the coating attachment fastness requirement on the metal finishing layer.The influence that the addition of maleic anhydride resin in prescription is bigger to being attached with of the coat of metal, addition be less than 5 weight portions, occurs the metal finishing pull-up easily after boiling hot to fall; Addition is greater than 10 weight portions, and thermoprint descends the phenomenon that adhesive tape test has point-like to come off to the attachment fastness of base material.The maleic anhydride copolymer resins that is suitable among the present invention includes but not limited to: the SMA1440F of Sartomer company, SMA3840FX etc.
The main effect of the polyvinyl butyral resin described in the present invention is to increase adhesion effect, and improves the viscosity of the thermoprint gum of preparation, with better adaptation coating process, improves the thermoprint attachment fastness to grounds such as ABS, PC, PMMA, PS simultaneously.The polyvinyl butyral resin addition is less than 4 weight portions; Viscosity and state influence to gum are little, can not improve coating process adaptability, and the polyvinyl butyral resin addition is greater than 8 weight portions; Side cut property to thermoprint is influential, and unsharp phenomenon appears in meticulous literal thermoprint.Being suitable for polyvinyl butyral resin of the present invention includes but not limited to: the B30H of Kuraray company, B60H etc.
Isocyanate resin described in the present invention is the HDI performed polymer; Its main effect is after the adhered layer coating; Realize crosslinking curing with maleic anhydride copolymer resins and polyvinyl butyral resin, and further crosslinked in the hot stamping process process, promote the thermoprint attachment fastness; And ostentatious wear-resisting and chemicals-resistant characteristic etc. after the raising thermoprint, be suitable for HDI performed polymer of the present invention and include but not limited to: the N3390 of Beyer Co., Ltd etc.
The present invention is through the cooperation between described thermoplastic acrylic resin, maleic anhydride copolymer resins and the polyvinyl butyral resin; And crosslinked through with an amount of isocyanate resin; Form and simultaneously good the adhering to thermoprint of decorative layer adhered to ABS, PMMA, PC, the good of PS; Adhesion effect has reached the effect that adopts chlorinated polyolefin resin or vinyl chloride-vinyl acetate resin, can effectively substitute chlorine-containing resins, has realized the purpose that adhered layer is non-halogen.
The effect of the aerosil described in the present invention is the covering that increases gum coating, and it is clear to promote that thermoprint is cut edge.
Solvent described in the present invention is the mixed solvent of butanone, ethyl acetate, and ratio is between 1:1～1:2, and the butanone ratio greater than 2:1, causes the thermoprint attachment fastness to descend greater than 1:1 or ethyl acetate ratio easily.
The thickness of the adhered layer 5 described in the present invention is the 1-2 micron, and thickness is less than 1 micron, and the thermoprint integrity degree of plastic cement wide area surface is had adverse effect, and thickness is greater than 2 microns, and the thermoprint definition that the meticulous lines of plastic cement are decorated descends.
Support among the present invention can adopt but be not limited to the PET film of thickness 12-30 micron.
Release layer among the present invention, sclerosis protective layer, metal finishing layer can adopt technique known.
Non-halogen transfer printing type decorating film provided by the invention can prepare through following method:
On support, be coated with release layer, coating sclerosis protective layer on release layer, evaporation metal decorative layer on the sclerosis protective layer is coated with adhered layer on the metal finishing layer, obtain non-halogen transfer printing type decorating film.
Below in conjunction with embodiment the present invention is further specified.
Embodiment 1
The parts by weight of each component are following in the adhered layer prescription:
(molecular weight is 60000 to thermoplastic acrylic resin LP65/12; 57 ℃ of Tg values) 16.0,
(molecular weight is 7000 to phenylethylene-maleic anhydride copolymer resins SMA1440F; Acid number is 165-200; 60 ℃ of Tg values) 10.0
Polyvinyl butyral resin B30H 8.0,
Isocyanate resin N3390 2.0,
Aerosil 4.0,
Butanone 20.0,
Ethyl acetate 40.0,
Adopt 20 microns PET films, 0.5 micron of coating release layer, 3 microns of sclerosis protective layers, metal finishing layer 60 nanometer, adhered layer thickness is 1 micron, obtains non-halogen transfer printing type decorating film.
On the non-halogen transfer printing type decorating film thermoprint ABS plastic spare that obtains, test each item performance.
Embodiment 2
Each composition weight umber is following in the adhered layer prescription:
(molecular weight is 60000 to thermoplastic acrylic resin LP65/11; 57 ℃ of Tg values) 8.0,
(molecular weight is 10500 to phenylethylene-maleic anhydride copolymer resins SMA3840F; Acid number is 95-120; 75 ℃ of Tg values) 5.0
Polyvinyl butyral resin B60H 4.0,
Isocyanate resin N3390 1.0,
Aerosil 2.0,
Butanone 30.0,
Ethyl acetate 50.0,
Adopt 20 microns PET films, 0.8 micron of coating release layer, 2.5 microns of sclerosis protective layers, evaporation metal decorative layer 40 nanometers, coating adhered layer thickness is 1.5 microns, obtains non-halogen transfer printing type decorating film.
On the non-halogen transfer printing type decorating film thermoprint ABS plastic spare that obtains, test each item performance.
Embodiment 3
Each composition weight umber is following in the adhered layer prescription:
(molecular weight is 60000 to thermoplastic acrylic resin LP65/12; 57 ℃ of Tg values) 12.0,
(molecular weight is 7000 to phenylethylene-maleic anhydride copolymer resins SMA1440F; Acid number is 165-200; 60 ℃ of Tg values) 8.0
Polyvinyl butyral resin B30H 6.0,
Isocyanate resin N3390 1.5,
Aerosil 2.5,
Butanone 30.0,
Ethyl acetate 40.0,
Adopt 22 microns PET films, 1 micron of coating release layer, 1.5 microns of sclerosis protective layers, evaporation metal decorative layer 50 nanometers, coating adhered layer thickness is 1.0 microns, obtains non-halogen transfer printing type decorating film.
On the non-halogen transfer printing type decorating film thermoprint ABS plastic spare that obtains, test each item performance.
Embodiment 4
Each composition weight umber is following in the adhered layer prescription:
(molecular weight is 60000 to thermoplastic acrylic resin LP65/12; 57 ℃ of Tg values) 14.0,
(molecular weight is 7000 to phenylethylene-maleic anhydride copolymer resins SMA1440F; Acid number is 165-200; 60 ℃ of Tg values) 6.0
Polyvinyl butyral resin B30H 6.0,
Isocyanate resin N3390 1.5,
Aerosil 2.5,
Butanone 30.0,
Ethyl acetate 40.0,
Adopt 22 microns PET films, 1 micron of coating release layer, 1.5 microns of sclerosis protective layers, evaporation metal decorative layer 50 nanometers, coating adhered layer thickness is 1.2 microns, obtains non-halogen transfer printing type decorating film.
On the non-halogen transfer printing type decorating film thermoprint ABS plastic spare that obtains, test each item performance.
Embodiment 5
Each composition weight umber is following in the adhered layer prescription:
(molecular weight is 60000 to thermoplastic acrylic resin LP65/12; 57 ℃ of Tg values) 10.0,
(molecular weight is 7000 to phenylethylene-maleic anhydride copolymer resins SMA1440F; Acid number is 165-200; 60 ℃ of Tg values) 7.5
Polyvinyl butyral resin B30H 8.0,
Isocyanate resin N3390 2.0,
Aerosil 2.5,
Butanone 30.0,
Ethyl acetate 40.0,
Adopt 22 microns PET films, 1 micron of coating release layer, 1.5 microns of sclerosis protective layers, evaporation metal decorative layer 50 nanometers, coating adhered layer thickness is 1.2 microns, obtains non-halogen transfer printing type decorating film:
On the non-halogen transfer printing type decorating film thermoprint ABS plastic spare that obtains, test each item performance.
In the table, the method for testing of each item performance is following:
1. content of halogen: firing method test.
2. thermoprint attachment fastness: hundred lattice methods, tape stripping test.
3. thermoprint definition: the standard printing plate is flat to scald.
4. ethanol-tolerant wiping number of times: the appearance of anti-solvent wiping the, heavy burden 750g.
5. case hardness: pencil hardness meter.
Claims (5)
1. non-halogen transfer printing type decorating film that is used for the plastic cement incrustation; It comprises: support, release layer, sclerosis protective layer, metal finishing layer and adhered layer; It is characterized in that the content of halogen in the said adhered layer is less than 600ppm, component that adhered layer contains and weight portion are:
8～16 parts of thermoplastic acrylic resins;
5～10 parts of maleic anhydride copolymer resinses;
4～8 parts of polyvinyl butyral resins;
1～2 part of isocyanate resin;
2～4 parts of aerosils;
60～80 parts of solvents.
2. decorating film according to claim 1 is characterized in that, described thermoplastic acrylic resin be molecular weight between 30000～70000, the Tg value is at 45 ℃～70 ℃ the methyl methacrylate and the copolymer of n-BMA.
3. decorating film according to claim 2 is characterized in that, described maleic anhydride copolymer resins is between 1000～20000, acid number 50～500, and the Tg value is at 50 ℃～80 ℃ maleic anhydride copolymer resins.
4. decorating film according to claim 3 is characterized in that, described solvent is the mixed solvent of butanone, ethyl acetate, its weight ratio 1:1～1:2.
5. decorating film according to claim 4 is characterized in that, the thickness of said adhered layer is 1～2 micron.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104403604A (en) * | 2014-11-04 | 2015-03-11 | 张桂华 | Stable thermosetting adhesive |
| CN104908380A (en) * | 2015-06-30 | 2015-09-16 | 保定乐凯新材料股份有限公司 | Transfer decoration film |
| CN105018016A (en) * | 2015-09-03 | 2015-11-04 | 侯颖 | Preparation method of high-strength adhesive composition for leather |
| CN105647435A (en) * | 2016-01-13 | 2016-06-08 | 广州慧谷工程材料有限公司 | Adhesive agent for IML and preparation method and application thereof |
| CN105667103A (en) * | 2016-03-04 | 2016-06-15 | 杭州兴甬复合材料有限公司 | Thermal transfer ribbon |
| CN109517542A (en) * | 2018-11-13 | 2019-03-26 | 香洋新材料（江苏）有限公司 | A kind of transfer film high grade of transparency ABS glue and preparation method thereof |
| CN110126409A (en) * | 2019-05-10 | 2019-08-16 | 保定乐凯新材料股份有限公司 | Multilayer film with metal wire-drawing effect layer |
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| CN101579972A (en) * | 2008-05-13 | 2009-11-18 | 台湾真空镀膜股份有限公司 | Metallic transfer printing film |
| CN102220096A (en) * | 2010-04-09 | 2011-10-19 | 日东电工株式会社 | Pressure-sensitive adhesive composition and acrylic pressure-sensitive adhesive tape |
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2012
- 2012-05-14 CN CN201210147957XA patent/CN102673287A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101579972A (en) * | 2008-05-13 | 2009-11-18 | 台湾真空镀膜股份有限公司 | Metallic transfer printing film |
| CN102220096A (en) * | 2010-04-09 | 2011-10-19 | 日东电工株式会社 | Pressure-sensitive adhesive composition and acrylic pressure-sensitive adhesive tape |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104403604A (en) * | 2014-11-04 | 2015-03-11 | 张桂华 | Stable thermosetting adhesive |
| CN104908380A (en) * | 2015-06-30 | 2015-09-16 | 保定乐凯新材料股份有限公司 | Transfer decoration film |
| CN105018016A (en) * | 2015-09-03 | 2015-11-04 | 侯颖 | Preparation method of high-strength adhesive composition for leather |
| CN105647435A (en) * | 2016-01-13 | 2016-06-08 | 广州慧谷工程材料有限公司 | Adhesive agent for IML and preparation method and application thereof |
| CN105667103A (en) * | 2016-03-04 | 2016-06-15 | 杭州兴甬复合材料有限公司 | Thermal transfer ribbon |
| CN109517542A (en) * | 2018-11-13 | 2019-03-26 | 香洋新材料（江苏）有限公司 | A kind of transfer film high grade of transparency ABS glue and preparation method thereof |
| CN110126409A (en) * | 2019-05-10 | 2019-08-16 | 保定乐凯新材料股份有限公司 | Multilayer film with metal wire-drawing effect layer |
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Application publication date: 20120919 |