CN105196778A - Decorative film - Google Patents
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- CN105196778A CN105196778A CN201510664722.1A CN201510664722A CN105196778A CN 105196778 A CN105196778 A CN 105196778A CN 201510664722 A CN201510664722 A CN 201510664722A CN 105196778 A CN105196778 A CN 105196778A
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Abstract
The invention discloses a decorative film which comprises a fluorine-modified film and a film-like substrate, wherein the fluorine-modified film and the substrate are adhered in a layered manner; the fluorine-modified film comprises a surface layer, a blocking layer and a bonding layer; the bonding layer, the blocking layer and the surface layer are outwards and sequentially adhered to the substrate from the substrate in a layered manner; the bonding layer is mainly prepared from a mixture of PVDF and resin A. The weather-resistant multilayer film disclosed by the invention is stable in structure, high in use environment tolerance, wide in application range, convenient for reduction of energy consumption of urban production and living and beneficial to environment friendliness.
Description
Technical field
The present invention relates to a kind of multilayer film, particularly a kind of decorating film.
Background technology
Building film material material is the New Building Materials grown up from 20 century 70s, belong to the coated fabric in field of textiles, the 5th kind of construction material after iron and steel, cement, timber and glass, it can in the inconvenient field of existing building materials application, as or ultra-large type architectural use large-scale without pillar, be provided with the superiority that traditional building material is incomparable, expand the range of application of construction material.It has the moulding advantages such as lightly free, attractive in appearance, printing opacity, energy-saving and environmental protection, excellent fire resistance, anti-fouling and self-cleaning performance, safe life be long, is widely used in the buildings such as large-scale stadium, shopping field, show ground, entrance gallery, public place of entertainment, parking lot, plant sightseeing dome and gas station mainly as semipermanent construction material.Because 2008 Beijing Olympic Games stadiums " Bird's Nest " etc. successfully build up and come into operation, and the holding of the international distinguished gathering such as Shanghai World's Fair and the Guangzhou Asian Games in 2010, the development at home of film material has entered a rapid growth period.Membrane material is the key of building membrane structure, and China's investigation and application is started late, and technical merit is lower, and most of membrane material also mainly relies on import.
Interior trim film internal and overseas also has larger gap, and the ability of domestic topical product or technology may possess, but is possessing in modular system Integrated Development ability and there is a big difference.Current this respect market all monopolize by some transnational suppliers.Domestic many car load factories, when developing new model, can invite these transnational Supplier involvement Synchronization Design exploitations, even by the integration being responsible for whole interior trim project, contribute to ensureing product quality and development management.
PVDF thin film is then the fastest kind of growing up in fluoro-containing copolymer film, and American market average growth rate per annum reaches 7.6%.At present, by PVDF thin film and PVC and PE Film laminated, while its performance of guarantee, the cost of product can be reduced.In addition, PVDF thin film and other films have good compatibility, and the popularization of plural layers is while its performance of maintenance, more economical.The development in PVDF thin film market mainly has benefited from the generally use of lithium battery.At present, the fast development of mobile phone, notebook computer, portable type electronic product, solar panel, building and automobile decoration film and semicon industry has promoted widely using of this kind of film.In addition, pvdf membrane is also just more and more for fields such as fuel cell, aircraft inside gadget and business automation equipments.PVDF and PVC composite membrane just has the market demand widely as a kind of building decoration film, and along with technological innovation in the market share of the outdoor films such as the fenestrated membrane of the developed countries such as America and Europe in occupation of more than 90%.
Ultraviolet irradiation (UV) absorbent is added in one deck of polymer film by existing weatherable films.But the ultraviolet radiation absorber of high concentration causes the mechanical performance of this polymer film to decline usually, and cause in polymer film muddy.In addition, previous author also finds, UV absorbent causes the performance of film to decline along with the time from the release polymer film.As a result, the service life of polymer film is restricted, and the substrate that it covers or assembly may be damaged along with the degraded of diaphragm.Therefore, a kind of weather resistant polymer film of improvement is needed.
Summary of the invention
For solving the problem, decorating film disclosed by the invention, have weatherability strong, ageing resistace is good, and mechanical performance is superior, not easily occurs damaged or peels off, and having the building decoration film of good wearability.
Decorating film disclosed by the invention, comprise fluorine-containing Modified Membrane and filmated base material, fluorine-containing Modified Membrane and base material layered are fitted, fluorine-containing Modified Membrane comprises surface layer, and (constitutive material of surface layer comprises the base material of 100 weight portions and the PTFE micro mist of 0-10 weight portion, PTFE micro mist is adopted not only to have good compatibility with matrix, PTFE micro mist can also strengthen surface layer simultaneously, thus improve the wearability of surface layer, strengthen weatherability), barrier layer and tack coat, tack coat, barrier layer and surface layer fit on base material by the outside sequentially layered of base material, surface layer material is fluorine-containing polymer, tack coat is polyacrylic acid adhesive layer, polyurethane adhesive layer, melt viscosity oxidant layer, epoxyn layer, one in the Blend rubber adhesive layer of organic silica gel adhesive layer and PVDF and Resin A, Resin A be one in the random copolymer of modified PMMA or nano modification copolyamide and ethene or both.Wherein the material of base material can be comprise single layer structure in PVC, PP, PE, PC, nylon, polyester or sandwich construction; During for sandwich construction, adjacent layer material can be different.
The one of decorating film disclosed by the invention is improved, and tack coat, barrier layer and surface layer are fitted on base material by the outside sequentially layered of base material in base material both sides.
The one of decorating film disclosed by the invention is improved, mainly consisting of (with weight parts) of barrier layer, PVDF40 ~ 100 part, ultraviolet absorber 0.1 ~ 1 part, flexibilizer 5 ~ 15 parts, antioxidant 0-1 part, cold-resistant agent 0-1 part.The auxiliary agent outer application all representing common auxiliary agent unless specified otherwise such as flexibilizer, antioxidant and weather resisting agent.
The one of decorating film disclosed by the invention is improved, modified PMMA 0 ~ 60 part that barrier layer also comprises (with weight parts).
The one of decorating film disclosed by the invention is improved, fluorine-containing polymer is blended polymer or copolymerization high polymer, the blend of one or more wherein in blended polymer fluorinated ethylene propylene FEP, ethylene-tetrafluoroethylene ETFE, polytetrafluoroethylene (PTFE)-perfluoro propyl vinyl ether PFA, polytetrafluoroethylene (PTFE)-perfluoro methyl vinyl ether MFA, polytetrafluoroethylene PTFE, polyvinylidene fluoride PVDF, polyethylene chlorotrifluoroethylene ECTFE, polychlorotrifluoroethylene PCTFE, polytetrafluoroethylene (PTFE)-hexafluoropropene-vinylidene fluoride THV polymer; Copolymerization high polymer (comprising without returning copolymer or homopolymers) is the one in fluorinated ethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoro propyl vinyl ether copolymer, tetrafluoroethylene-perfluoro methyl vinyl ether copolymer, tetrafluoroethene-vinylidene fluoride copolymer, ethylene-chlorotrifluoro-ethylene copolymer, propylene-chlorotrifluoroethylcopolymer copolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymer.Surface layer is preferably, and the raw material of surface layer consists of the PTFE micro mist of the base material of 100 weight portions (base material is above-mentioned fluorine-containing polymer) and 0-10 weight portion.Adopt PTFE micro mist to be conducive to improving surface abrasion resistance and the self-cleaning performance of surface layer, while continuity decorating film service life, make its more easy care.
The one of decorating film disclosed by the invention is improved, mainly consisting of (with weight parts) of tack coat, the random copolymer 80 ~ 100 parts of nano modification copolyamide and ethene, PVDF0 ~ 20 part.Wherein the random copolymer of nano modification copolyamide and ethene is the random copolymer with the copolyamide of nano material (comprising nanofiber or nanoparticle etc.) modification and ethene.
The one of decorating film disclosed by the invention is improved, mainly consisting of (with weight parts) of tack coat, modified PMMA 80 ~ 100 parts, PVDF0 ~ 20 part.In the present invention modified PMMA refer to PMMA material for the requirement of decorating film different and improving routinely in printing opacity, intensity, fire-retardant, anti-aging and polishing machine etc. of making.
Decorating film disclosed by the invention, surface layer adopts fluorinated polymer material to have lower surface tension, thus has antifouling self-cleaning property, and rainwater can wash away the attachment on film surface; Barrier layer can intercept ultraviolet and steam etc., thus plays the effect of protection base material; Tack coat makes base material and diaphragm can be good at laminating, and long-time use is not vulnerable to the osmosis of pollution, does not come off, does not wrinkle.
Resistance to soiling: spot easy cleaning is removed to the difficulty such as oil smoke, oiliness pen and ink, and not by time restriction, pollute for a long time and still easily cleaned, can not adhere on decorating film;
Chemical inertness: can the acid-base solution of resistance to PH1 ~ 14, is insoluble to the organic solvents such as alcohol, aldehyde, benzene;
Wearability: compared with traditional interior trim film, its mar proof improves a lot;
The feature of environmental protection: there is excellent barrier property, have high barrier to the VOC gas (organic gas) that base material at high temperature discharges, close to zero percent of pass, pernicious gas cannot enter indoor and cause damage to human body;
Weatherability: fluorine-contained film is due to its splendid weatherability and light aging resisting property, and building is widely used out of doors, and its life-span, more than 15 years, can extend the service life of traditional interior trim film.
Accompanying drawing explanation
The comparison diagram of film in the light transmission of Fig. 1, decorating film disclosed by the invention and prior art;
The comparison diagram of film in the resistance to ag(e)ing of Fig. 2, decorating film disclosed by the invention and prior art, wherein sample A:PVC base material film; Sample B: composite membrane (weatherable films 30 μm); Sample C: composite membrane (weatherable films 50 μm).
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, illustrate the present invention further, following detailed description of the invention should be understood and be only not used in for illustration of the present invention and limit the scope of the invention.It should be noted that, the word "front", "rear" of use is described below, "left", "right", "up" and "down" refer to direction in accompanying drawing, word " interior " and " outward " refer to the direction towards or away from particular elements geometric center respectively.
Constructive embodiment 1
Decorating film in the embodiment of the present invention, comprise fluorine-containing Modified Membrane and membranaceous base material, fluorine-containing Modified Membrane and base material layered are fitted, and fluorine-containing Modified Membrane comprises surface layer, barrier layer and tack coat, and tack coat, barrier layer and surface layer are fitted on base material by the outside sequentially layered in base material side.
Constructive embodiment 2
Decorating film in the embodiment of the present invention, comprise fluorine-containing Modified Membrane and membranaceous base material, fluorine-containing Modified Membrane and base material layered are fitted, and fluorine-containing Modified Membrane comprises surface layer, barrier layer and tack coat, and tack coat, barrier layer and surface layer are fitted on base material by the outside sequentially layered of base material in base material both sides.
Below about the embodiment of the material of each surface layer is all applicable to each layer of constructive embodiment 1-2, and the difference of its material kind does not affect character and the performance of decorating film of the presently claimed invention.
In following examples, the surface layer of multilayer film all adopts fluorine-containing blended polymer or copolymerization high polymer, wherein blended polymer fluorinated ethylene propylene FEP, ethylene-tetrafluoroethylene ETFE, polytetrafluoroethylene (PTFE)-perfluoro propyl vinyl ether PFA, polytetrafluoroethylene (PTFE)-perfluoro methyl vinyl ether MFA, polytetrafluoroethylene PTFE, polyvinylidene fluoride PVDF, polyethylene chlorotrifluoroethylene ECTFE, polychlorotrifluoroethylene PCTFE, the blend of one or more in polytetrafluoroethylene (PTFE)-hexafluoropropene-vinylidene fluoride THV polymer is (as fluorinated ethylene propylene FEP and ethylene-tetrafluoroethylene ETFE, polytetrafluoroethylene (PTFE)-perfluoro propyl vinyl ether PFA, polytetrafluoroethylene (PTFE)-perfluoro methyl vinyl ether MFA, polytetrafluoroethylene PTFE, polyvinylidene fluoride PVDF, polyethylene chlorotrifluoroethylene ECTFE, polychlorotrifluoroethylene PCTFE, in polytetrafluoroethylene (PTFE)-hexafluoropropene-vinylidene fluoride THV polymer, at least one is blended, this place embodiment scheme is numerous, here do not enumerate, but there is polymer in this place through blended all feasible schemes all in required scope, lower same), copolymerization high polymer is the one in fluorinated ethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoro propyl vinyl ether copolymer, tetrafluoroethylene-perfluoro methyl vinyl ether copolymer, tetrafluoroethene-vinylidene fluoride copolymer, ethylene-chlorotrifluoro-ethylene copolymer, propylene-chlorotrifluoroethylcopolymer copolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymer.Surface layer can also formerly state fluorine-containing blended polymer or copolymerization high polymer be base material 100 weight portion technically add 0-10 weight portion again PTFE micro mist (PTFE micro mist consumption can be 1,2,3,4,5,6,7,8,9,10 and 0-19 weight portion within the scope of other arbitrary value).When in face stock containing multiple in fluorine-containing blended polymer or copolymerization high polymer time, multiple fluorine-containing polymer consist of any ratio.Surface layer adopts when above-mentioned blended polymer or copolymerization high polymer and decorates membrane technology scheme all within the scope of protection of present invention, and does not exceed its restriction.
Barrier layer embodiment 1
The consisting of (with weight parts) of barrier layer in the present embodiment, PVDF40 part, ultraviolet absorber 0.3 part, flexibilizer 5 parts, cold-resistant agent 1 part.
Barrier layer embodiment 2
The consisting of (with weight parts) of barrier layer in the present embodiment, PVDF50 part, ultraviolet absorber 0.5 part, flexibilizer 12 parts, 1 part, antioxidant.
Barrier layer embodiment 3
The consisting of (with weight parts) of barrier layer in the present embodiment, PVDF60 part, ultraviolet absorber 0.8 part, flexibilizer 15 parts, 0.1 part, antioxidant, cold-resistant agent 0.5 part.
Barrier layer embodiment 4
The consisting of (with weight parts) of barrier layer in the present embodiment, PVDF70 part, ultraviolet absorber 0.25 part, flexibilizer 10 parts, 0.3 part, antioxidant, cold-resistant agent 0.3 part.
Barrier layer embodiment 5
The consisting of (with weight parts) of barrier layer in the present embodiment, PVDF80 part, ultraviolet absorber 0.2 part, flexibilizer 6 parts, 0.9 part, antioxidant, cold-resistant agent 0.4 part.
Barrier layer embodiment 6
The consisting of (with weight parts) of barrier layer in the present embodiment, PVDF90 part, ultraviolet absorber 1 part, flexibilizer 10.7 parts, 0.8 part, antioxidant, cold-resistant agent 0.9 part.
Barrier layer embodiment 7
The consisting of (with weight parts) of barrier layer in the present embodiment, PVDF100 part, ultraviolet absorber 0.7 part, flexibilizer 8.5 parts, 0.4 part, antioxidant, cold-resistant agent 0.3 part.
Barrier layer embodiment 8
The consisting of (with weight parts) of barrier layer in the present embodiment, PVDF55 part, ultraviolet absorber 0.23 part, flexibilizer 13.1 parts, 0.5 part, antioxidant, cold-resistant agent 0.2 part.
Barrier layer embodiment 9
The consisting of (with weight parts) of barrier layer in the present embodiment, PVDF67 part, ultraviolet absorber 0.6 part, flexibilizer 6.2 parts, 0.65 part, antioxidant, cold-resistant agent 0.6 part.
Barrier layer embodiment 10
The consisting of (with weight parts) of barrier layer in the present embodiment, PVDF49 part, ultraviolet absorber 0.9 part, flexibilizer 9.1 parts, 0.32 part, antioxidant, cold-resistant agent 0.7 part.
The difference of barrier layer embodiment 11-20 and barrier layer embodiment 1-10 is only:
(consumption of modified PMMA can be modified PMMA 60 parts that barrier layer also comprises (with weight parts) in addition, with weight parts, 1,3,5,7,10,12,15,19,20,22,25,28,30,32,35,38,40,43,45,50,55,59 and 0-60 part within the scope of other value).
Include, without being limited in above barrier layer embodiment technical scheme, technical characteristic PVDF can also carry out equivalent replacement with blended polymer or copolymerization high polymer, wherein blended polymer fluorinated ethylene propylene FEP, ethylene-tetrafluoroethylene ETFE, polytetrafluoroethylene (PTFE)-perfluoro propyl vinyl ether PFA, polytetrafluoroethylene (PTFE)-perfluoro methyl vinyl ether MFA, polytetrafluoroethylene PTFE, polyvinylidene fluoride PVDF, polyethylene chlorotrifluoroethylene ECTFE, polychlorotrifluoroethylene PCTFE, the blend of one or more in polytetrafluoroethylene (PTFE)-hexafluoropropene-vinylidene fluoride THV polymer, copolymerization high polymer is the one in fluorinated ethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoro propyl vinyl ether copolymer, tetrafluoroethylene-perfluoro methyl vinyl ether copolymer, tetrafluoroethene-vinylidene fluoride copolymer, ethylene-chlorotrifluoro-ethylene copolymer, propylene-chlorotrifluoroethylcopolymer copolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymer.
Tack coat embodiment 1
The consisting of (with weight parts) of tack coat in the present embodiment, the random copolymer of nano modification copolyamide and ethene 80 parts.
Tack coat embodiment 2
The consisting of (with weight parts) of tack coat in the present embodiment, nanometer improves random copolymer 85 parts, PVDF5 part of copolyamide and ethene.
Tack coat embodiment 3
The consisting of (with weight parts) of tack coat in the present embodiment, the random copolymer 90 parts of copolyamide and ethene, PVDF20 part.
Tack coat embodiment 4
The consisting of (with weight parts) of tack coat in the present embodiment, the random copolymer 95 parts of copolyamide and ethene, PVDF10 part.
Tack coat embodiment 5
The consisting of (with weight parts) of tack coat in the present embodiment, the random copolymer 100 parts of copolyamide and ethene, PVDF15 part.
In tack coat embodiment 1-5 (with weight parts), the random copolymer of copolyamide and ethene can also be 82,84,88,91,93,97 and 80-100 within the scope of the weight portion of other arbitrary value; PVDF can also be 1,4,7,9,12,17,19 and 0-20 within the scope of the weight portion of other arbitrary value.
Tack coat embodiment 6
The consisting of (with weight parts) of tack coat in the present embodiment, modified PMMA 80 parts, PVDF3 part.
Tack coat embodiment 7
The consisting of (with weight parts) of tack coat in the present embodiment, modified PMMA 87 parts, PVDF20 part.
Tack coat embodiment 8
The consisting of (with weight parts) of tack coat in the present embodiment, modified PMMA 90 parts, PVDF10 part.
Tack coat embodiment 9
The consisting of (with weight parts) of tack coat in the present embodiment, modified PMMA 93 parts.
Tack coat embodiment 10
The consisting of (with weight parts) of tack coat in the present embodiment, modified PMMA 100 parts, PVDF18 part.
In tack coat embodiment 6-10 (with weight parts), modified PMMA can also be 82,85,88,91,95,97 and 80-100 within the scope of the weight portion of other arbitrary value; PVDF can also be 1,5,7,9,12,15,19 and 0-20 within the scope of the weight portion of other arbitrary value.
Tack coat can also for polyacrylic acid adhesive layer, polyurethane adhesive layer, melt viscosity oxidant layer, epoxyn layer, organic silica gel adhesive layer be using as the alternative including, without being limited to above-mentioned tack coat embodiment technical scheme.
In all embodiments of the present invention program, Base Material comprises single layer structure in PVC, PP, PE, PC, nylon, polyester or sandwich construction, during for sandwich construction, adjacent layer material can be different, when adjacent layer is different, such as adjacent two layers is PVC/PP, PVC/PE, PVC/PC, PVC/ nylon, PVC/ polyester, PP/PE, PP/PC, PP/ nylon, PP/ polyester, PE/PC, PE/ nylon, PE/ polyester, PC/ nylon, PC/ polyester, (wherein nylon includes, without being limited to common nylon 6 to nylon/polyester, NYLON610, nylon66 fiber, nylon 612, nylon 11, nylon 8, arbitrary in nylon 9 etc., polyester includes, without being limited to PET, polybutylene terephthalate, arbitrary in polyarylate etc.), this place "/" only represents that the layer of adjacent two layers connects relation and do not express level and the direction position relationship of each layer.
The testing example 1 of the decorating film of the present invention jointly formed for PVC with constructive embodiment 1, barrier layer embodiment 1 and tack coat embodiment 1, base material below and the testing example 2 of decorating film of the present invention jointly formed for PP for constructive embodiment 2, barrier layer embodiment 2 and tack coat embodiment 2, base material are tested, and the superiority of decorating film of the present invention is described:
As following table:
Table one performance test conditions
The performance table of comparisons of table two and comparative example
Test specification
Chemical resistance is tested:
Sample: adopt this testing example decorating film 100 and existing commercial membrane 100 respectively, film surface can be smooth also can for by decorative pattern, all with the soft material of oiliness at film surface pattern (if oil fountain pen is at film surface label).
Test mode (arbitraryly or multiple jointly to carry out below, multiple jointly carry out each test sequence do not limit): (1) ethanol infiltrates 24h; (2) salt fog (5%/40 DEG C) 1 week; (3) water infiltration 10 days;
Result:
Commercial membrane: sample appearance significant change, fold, surfaces of tacky, writing indicates and infiltrates through basement membrane, swoons and opens.
This testing example decorating film: sample appearance is without significant change, and not delamination corrugationless, is not clamminess, writing indicates cannot infiltrate basement membrane.
Soil release performance is tested:
Sample: adopt this testing example decorating film 100 and existing commercial membrane 100 respectively, film surface can be smooth also can for by decorative pattern, all with the soft material of oiliness at film surface pattern (if oil fountain pen is at film surface label).
Test mode: the marking is all done respectively with oil pen and free ink pen in sample film surface on sample, cleans with ethanol after 24h.
Result:
Commercial membrane: sample appearance is without significant change, and oiliness writing indicates and infiltrates through basement membrane, swoons and opens.
This testing example decorating film: sample appearance is without significant change, and writing indicates cannot infiltrate basement membrane.
Wearability test:
Sample: adopt this testing example decorating film 100 and existing commercial membrane 100 respectively, film surface can be smooth also can for by decorative pattern, all with the soft material of oiliness at film surface pattern (if oil fountain pen is at film surface label).
Test mode: the marking is all done respectively with oil pen and free ink pen in sample film surface on sample, cleans with ethanol after 24h, with cleaning ball wiping 1000 times, then uses ethanol clean surface.
Result:
Commercial membrane: sample appearance has obvious cut variable color, forms burr, and deformation occurs, and forms pollution.
Routine decorating film is executed in this actual measurement examination: sample appearance is without significant change, and slightly deformation, keeps clean.
Light-proofness is tested
As shown in Figure 1, this testing example 1 decorating film can be seen, to the light that wavelength is 200-360nm, there is obvious barriering effect.
Burn-in test
As shown in Figure 2, under equal conditions, after 3000h xenon lamp aging, aging speed aggravates for this testing example 1 decorating film and commercial membrane, and commercial membrane jaundice variable color is obvious, and the present invention's aging speed after irradiation 3000h is still comparatively slow, there is good ageing resistace.
As shown in above-mentioned testing example 1 and testing example 2, comparably, all embodiments of the present invention all meet following performance through test:
1, stability: the decorating film of 150 ㎜ × 150 ㎜ is attached on the aluminium sheet of 200 ㎜ × 200 ㎜, centre carves the cross of 100 ㎜ × 100 ㎜ wherein, places after 48 hours, maximal clearance≤0.3 ㎜ of cross at 65 DEG C.
Operative norm GB/T2423.2-2008.
2, weatherability: with the test machine of daylight charcoal element arc light lamp-based, under irradiating through more than 300 hours, decorating film is unchanged
3, cohesive force: be attached in test sample plate by the belt decorative film of 25 ㎜ × 180 ㎜, places after 24 hours at 20 DEG C, on testing machine with 300 ㎜/point speed, to the direction of 180 degree, pull decorating film, carry out bonding force test:
Operative norm: GB/T2792-1998
4, heat resistance: place 30 days in 65 DEG C of environment, bonding force is without exception.
5, cold resistance: place 72 hours in-40 DEG C of environment, bonding force is without exception.
6, moisture-proof: at 40 DEG C, place 30 days in 95% humidity environment, bonding force is without exception.
7, low-temperature impact resistance: at 0 DEG C of temperature, highly freely falls the steel ball of 100g from 125 ㎜, and impact the decorating film that thick 1.0 ㎜ aluminium sheets are applied ointment or plaster, decorating film crack-free is without coming off.
Operative norm: GB/T2423.8-1995
8, wearability: use wear test machine (taberabraser, abrasion wheels CS-17, weight 1.0 ㎏) to go round and round a millstone 5000 turns, decorating film superficial makings is unchanged
Operative norm: GB/T1768-2006
9, drug resistance, solvent resistance: rinse through water after specimen surface drips following medicine, watch or clock glass lid 6h, then at room temperature place 24h observation surface condition; Benzinum, alcohol, n-acetic acid, cresols, ammoniacal liquor, hydrochloric acid (10%), caustic soda (10%): unchanged
10, chemical-resistant: decorating film is soaked in following chemicals after being attached to aluminium sheet upper 72 hour:
11, stain resistance: after contacting 24h with following material, observe surface condition with after neutral detergent or alcohol wipe:
(1) after contacting 24h with vinegar, coffee, soy sauce, catsup, lemon juice, grape wine, cola, black tea, yogurt, Xi Shui (1%), soda, formalin, milk, hydrochloric acid (10%), alcohol (50%), family expenses ammonia, salt solution (1%) material, observe surface condition with after neutral detergent or alcohol wipe, do not stay spot;
(2) water-based signature pen, wax crayon can wash away with alcohol.
12, fire protecting performance: operative norm: TB/T3237-2010
Scope: flammability, smokiness, toxicity
Index: oxygen index (OI) (%) >=32
Flammability level: A
After burning, harmful gas concentration and smoke density index meet table 3 in TB/T3237-2010, table 4 requirement
13, environmental-protecting performance: perform: " structural material limits of harmful substances " in TB/T3139-2006 " rolling stock built-in material and room air limits of harmful substances ".
When not exceeding technical scope of the presently claimed invention, in all technical schemes of the present invention, base material material (including, without being limited to the technical scheme cited by above embodiment) can also be the single layer structure in PP, PE, PC, nylon, polyester or sandwich construction; When base material is sandwich construction, adjacent layer material can be different.
In view of the present invention program's embodiment is numerous, each embodiment experimental data is huge numerous, be not suitable for particularize explanation herein, but the content of the required checking of each embodiment is all close with the final conclusion obtained, so do not illustrate one by one the checking content of each embodiment, only with above-mentioned section Example, the excellent part of the present patent application is representatively described herein.When relating to the different testing scheme of same index, what adopt the present invention program to point out is arbitrary all passable, and does not all exceed in the scope of protection of present invention.
The technical scope midrange non-limit part that this place embodiment is protected application claims and in embodiment technical scheme to the new technical scheme that the equal replacement of single or multiple technical characteristic is formed, equally all in the scope of protection of present invention; Simultaneously in all embodiments enumerated or do not enumerate of the present invention program, parameters in the same embodiment only represents an example (i.e. a kind of feasible scheme) of its technical scheme, and between parameters, there is not strict cooperation and qualified relation, wherein each parameter can be replaced, except special declaration mutually when stating ask without prejudice to axiom and the present invention.
Technological means disclosed in the present invention program is not limited only to the technological means disclosed in above-mentioned technological means, also comprises the technical scheme be made up of above technical characteristic.The above is the specific embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (7)
1. a decorating film, comprise fluorine-containing Modified Membrane and filmated base material, described fluorine-containing Modified Membrane and base material layered are fitted, it is characterized in that: described fluorine-containing Modified Membrane comprises surface layer, barrier layer and tack coat, described tack coat, barrier layer and surface layer fit on base material by the outside sequentially layered of base material, described surface layer material is fluorine-containing polymer, described tack coat is polyacrylic acid adhesive layer, polyurethane adhesive layer, melt viscosity oxidant layer, epoxyn layer, one in the Blend rubber adhesive layer of organic silica gel adhesive layer and PVDF and Resin A, described Resin A be one in the random copolymer of modified PMMA or nano modification copolyamide and ethene or both.
2. decorating film according to claim 1, is characterized in that: described tack coat, barrier layer and surface layer are fitted on base material by the outside sequentially layered of base material in base material both sides.
3. decorating film according to claim 1 and 2, it is characterized in that: mainly consisting of (with weight parts) of described barrier layer, fluorine-containing polymer 40 ~ 100 parts, ultraviolet absorber 0.1 ~ 1 part, flexibilizer 5 ~ 15 parts, antioxidant 0-1 part, cold-resistant agent 0-1 part.
4. decorating film according to claim 3, is characterized in that: described barrier layer also comprises (with weight parts) modified PMMA 0 ~ 60 part.
5. decorating film according to claim 3, it is characterized in that: described fluorine-containing polymer is blended polymer or copolymerization high polymer, the blend of one or more wherein in blended polymer fluorinated ethylene propylene FEP, ethylene-tetrafluoroethylene ETFE, polytetrafluoroethylene (PTFE)-perfluoro propyl vinyl ether PFA, polytetrafluoroethylene (PTFE)-perfluoro methyl vinyl ether MFA, polytetrafluoroethylene PTFE, polyvinylidene fluoride PVDF, polyethylene chlorotrifluoroethylene ECTFE, polychlorotrifluoroethylene PCTFE, polytetrafluoroethylene (PTFE)-hexafluoropropene-vinylidene fluoride THV polymer; Copolymerization high polymer is the one in fluorinated ethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoro propyl vinyl ether copolymer, tetrafluoroethylene-perfluoro methyl vinyl ether copolymer, tetrafluoroethene-vinylidene fluoride copolymer, ethylene-chlorotrifluoro-ethylene copolymer, propylene-chlorotrifluoroethylcopolymer copolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymer.
6. decorating film according to claim 1 and 2, is characterized in that: mainly consisting of (with weight parts) of described tack coat, the random copolymer 80 ~ 100 parts of nano modification copolyamide and ethene, PVDF0 ~ 20 part.
7. decorating film according to claim 1 and 2, is characterized in that: mainly consisting of (with weight parts) of described tack coat, modified PMMA 80 ~ 100 parts, PVDF0 ~ 20 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510664722.1A CN105196778A (en) | 2015-10-15 | 2015-10-15 | Decorative film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510664722.1A CN105196778A (en) | 2015-10-15 | 2015-10-15 | Decorative film |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106592895A (en) * | 2016-11-24 | 2017-04-26 | 浙江歌瑞新材料有限公司 | Weather-proof adhesive sticker type polyvinyl chloride wallpaper |
| CN106626649A (en) * | 2016-11-24 | 2017-05-10 | 浙江歌瑞新材料有限公司 | Polyvinyl chloride floor resistant to stain and easy to clean as well as preparation process of polyvinyl chloride floor |
| CN106634661A (en) * | 2016-11-24 | 2017-05-10 | 浙江歌瑞新材料有限公司 | Weather-proof film for plastic floor |
| CN106677453A (en) * | 2016-11-24 | 2017-05-17 | 浙江歌瑞新材料有限公司 | Weather-proof polyvinyl chloride wallpaper and preparation process thereof |
| CN108883617A (en) * | 2016-04-01 | 2018-11-23 | 3M创新有限公司 | Multi-layer fluoropolymer films |
| CN109249654A (en) * | 2018-07-13 | 2019-01-22 | 浙江歌瑞新材料有限公司 | Protective film and its manufacturing process in a kind of van-type container car |
| CN109263204A (en) * | 2018-07-13 | 2019-01-25 | 浙江歌瑞新材料有限公司 | A kind of film-covered metal plate and its manufacturing process of highly corrosion resistant |
| CN110157346A (en) * | 2019-05-06 | 2019-08-23 | 费植煌 | A kind of decorating film of containing graphene |
| CN112313075A (en) * | 2018-06-13 | 2021-02-02 | Ａｇｃ株式会社 | Decorative film, method for producing decorative film, and method for producing three-dimensional molded article with decorative film |
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| FR2842529A1 (en) * | 2002-07-17 | 2004-01-23 | Atofina | Composition useful for producing coextruded polyvinylidene fluoride (PVDF) films comprises PVDF, polymethyl methacrylate, acrylic elastomer and ultraviolet absorber |
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| FR2842529A1 (en) * | 2002-07-17 | 2004-01-23 | Atofina | Composition useful for producing coextruded polyvinylidene fluoride (PVDF) films comprises PVDF, polymethyl methacrylate, acrylic elastomer and ultraviolet absorber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108883617A (en) * | 2016-04-01 | 2018-11-23 | 3M创新有限公司 | Multi-layer fluoropolymer films |
| US11254104B2 (en) | 2016-04-01 | 2022-02-22 | 3M Innovative Properties Company | Multilayer fluoropolymer films |
| CN108883617B (en) * | 2016-04-01 | 2020-09-15 | 3M创新有限公司 | Multilayer fluoropolymer films |
| US10662345B2 (en) | 2016-11-24 | 2020-05-26 | Zhejiang Green New Materials Co., Ltd. | High stain resistance and easy cleaning polyvinyl chloride floor and preparation process thereof |
| US20180142115A1 (en) * | 2016-11-24 | 2018-05-24 | Zhejiang Green New Materials Co.,LTD | High stain resistance and easy cleaning polyvinyl chloride floor and preparation process thereof |
| CN106677453A (en) * | 2016-11-24 | 2017-05-17 | 浙江歌瑞新材料有限公司 | Weather-proof polyvinyl chloride wallpaper and preparation process thereof |
| CN106592895A (en) * | 2016-11-24 | 2017-04-26 | 浙江歌瑞新材料有限公司 | Weather-proof adhesive sticker type polyvinyl chloride wallpaper |
| CN106634661A (en) * | 2016-11-24 | 2017-05-10 | 浙江歌瑞新材料有限公司 | Weather-proof film for plastic floor |
| CN106626649A (en) * | 2016-11-24 | 2017-05-10 | 浙江歌瑞新材料有限公司 | Polyvinyl chloride floor resistant to stain and easy to clean as well as preparation process of polyvinyl chloride floor |
| CN112313075A (en) * | 2018-06-13 | 2021-02-02 | Ａｇｃ株式会社 | Decorative film, method for producing decorative film, and method for producing three-dimensional molded article with decorative film |
| CN112313075B (en) * | 2018-06-13 | 2022-10-18 | Ａｇｃ株式会社 | Decorative film, method for producing decorative film, and method for producing three-dimensional molded article with decorative film |
| CN109249654A (en) * | 2018-07-13 | 2019-01-22 | 浙江歌瑞新材料有限公司 | Protective film and its manufacturing process in a kind of van-type container car |
| CN109263204A (en) * | 2018-07-13 | 2019-01-25 | 浙江歌瑞新材料有限公司 | A kind of film-covered metal plate and its manufacturing process of highly corrosion resistant |
| CN110157346A (en) * | 2019-05-06 | 2019-08-23 | 费植煌 | A kind of decorating film of containing graphene |
| CN110157346B (en) * | 2019-05-06 | 2021-05-07 | 费植煌 | Decoration film containing graphene |
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