CN105291499A - PE or PVC base material decoration film - Google Patents

PE or PVC base material decoration film Download PDF

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Publication number
CN105291499A
CN105291499A CN201510665152.8A CN201510665152A CN105291499A CN 105291499 A CN105291499 A CN 105291499A CN 201510665152 A CN201510665152 A CN 201510665152A CN 105291499 A CN105291499 A CN 105291499A
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China
Prior art keywords
base material
pvc
fluorine
film
tack coat
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Pending
Application number
CN201510665152.8A
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Chinese (zh)
Inventor
徐洪
徐诚
蒋晓璐
许锡均
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ZHEJIANG GREEN NEW MATERIALS CO Ltd
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ZHEJIANG GREEN NEW MATERIALS CO Ltd
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Priority to CN201510665152.8A priority Critical patent/CN105291499A/en
Publication of CN105291499A publication Critical patent/CN105291499A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16Homopolymers or copolymers or vinylidene fluoride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • C08L33/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12Homopolymers or copolymers of methyl methacrylate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12Homopolymers or copolymers of methyl methacrylate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/022 layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/24All layers being polymeric
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554Wear resistance
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/724Permeability to gases, adsorption
    • B32B2307/7242Non-permeable
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/754Self-cleaning
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00Decorative or ornamental articles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/14Gas barrier composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a PE or PVC base material decoration film. The PE or PVC base material decoration film comprises a fluorine-containing modified film and a lamellar base material made of PE or PVC. The fluorine-containing modified film and the base material are attached in a laminated mode. The fluorine-containing modified film comprises a surface layer, a barrier layer and a bonding layer, the bonding layer, the barrier layer and the surface layer are sequentially attached to the base material in a laminated mode from the base material to the outside, the surface layer is made of a fluorine-containing high polymer, the bonding layer is a PVC adhesive layer or a blended adhesive layer of PVDF and resin A, and the resin A is modified PMMA or/and a random copolymer of nano-modified copolyamide and ethylene. The decoration film is stable in structure, high in use environment tolerance, wide in application range and beneficial for lowering energy consumption of city production and living and protecting the environment.

Description

A kind of PE or PVC base decorating film
Technical field
The present invention relates to a kind of Multilayer decorative film, particularly a kind of PE or PVC base 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, PE disclosed by the invention or PVC base decorating film, 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.
PE disclosed by the invention or PVC base decorating film, comprise the filmated base material of fluorine-containing Modified Membrane and PVC 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 the one in the Blend rubber adhesive layer of PVC 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.
The one of PE disclosed by the invention or PVC base decorating film 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 PE disclosed by the invention or PVC base decorating film 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 PE disclosed by the invention or PVC base decorating film is improved, modified PMMA 0 ~ 60 part that barrier layer also comprises (with weight parts).
The one of PE disclosed by the invention or PVC base decorating film is improved, one or both in fluorine-containing polymer PVDF, PTFE, PFA, PCTFE.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 be in fluorine-containing polymer PVDF, PTFE, PFA, PCTFE one or both) 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 PE disclosed by the invention or PVC base decorating film is improved, mainly consisting of (with weight parts) of tack coat, random copolymer 80-100 part 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 PE disclosed by the invention or PVC base decorating film 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.
PE disclosed by the invention or PVC base decorating film, surface layer adopts fluorinated polymer material to have lower surface tension, thus has antifouling capacity; 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, PE disclosed by the invention or PVC base decorating film and prior art;
The comparison diagram of film in the resistance to ag(e)ing of Fig. 2, PE disclosed by the invention or PVC base decorating film and prior art, wherein sample A:PE or PVC base film; Sample B: composite membrane (fluorine-containing Modified Membrane 30 μm); Sample C: decorating film (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.
Surface for PVDF surface or PTFE surface or PFA surface or PCTFE surface or PVDF/PTFE surface or PVDF/PFA surface or PVDF/PCTFE surface or PTFE/PFA surface or PTFE/PCTFE surface of PFA/PCTFE surface or as the backing material PVDF100 weight and PTFE powder 1 based on the material of the weight of a surface or PTFE100 weight and PTFE powder 2 based on the material of the weight of a surface or PFA100 weight and PTFE powder 3 based on the material of the weight of a surface or PCTFE100 weight and PTFE micro powder 4 weight of a surface or as the backing material PVDF/PTFE100 weight and PTFE powder 5 weight of a surface or as the backing material PVDF/PFA100 weight and PTFE powder 5 weight of a surface or as the backing material PVDF/PCTFE100 weight and PTFE powder 6 based on the material of the weight of a surface or PTFE/PFA100 weight and PTFE powder 10 based on the material of the weight of a surface or PTFE and PTFE powder/PCTFE100 weight 9 based on the material of the weight of a surface or PFA/PCTFE100 weight and PTFE powder 8 weight of the surface.When in face stock containing in PVDF, PTFE, PFA, PCTFE two kinds time, two kinds of fluorine-containing polymers consist of any ratio.The enforcement of technical solution of the present invention is all met with the scheme of upper layer.
Constructive embodiment 1
PE or PVC base decorating film in the embodiment of the present invention, comprise fluorine-containing Modified Membrane and the membranaceous base material of PE or PVC material, fluorine-containing Modified Membrane and base material layered are fitted, 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
PE or PVC base decorating film in the embodiment of the present invention, comprise fluorine-containing Modified Membrane and the membranaceous base material of PE or PVC material, fluorine-containing Modified Membrane and base material layered are fitted, 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.
Here no matter base material material is adopt PE material or the performance of PVC material to the present invention's scope required for protection and decorating film product all can not have a negative impact, and the base material of PE material or PVC material can be replaced comparably in the present invention program.
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 the one in PVDF, PTFE, PFA, PCTFE.Surface layer adopts during above-mentioned material 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 replace with the one in PTFE, PFA, PCTFE is equivalent.
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 PVC adhesive layer be using as the alternative including, without being limited to tack coat embodiment 1-10 technical scheme.
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 PE 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
Wherein peel strength is the test value after decorating film of the present invention and aluminium sheet are fitted.
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, 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.
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 150mm × 150mm is attached on the aluminium sheet of 200mm × 200mm, centre carves the cross of a 100mm × 100mm wherein, places after 48 hours, the maximal clearance≤0.3mm 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: the belt decorative film of 25mm × 180mm is attached in test sample plate, place after 24 hours at 20 DEG C, with the speed that 300mm/ divides on testing machine, 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 125mm, and impact the decorating film that thick 1.0mm aluminium sheet is 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 ".
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 PE or PVC base decorating film, comprise the filmated base material of fluorine-containing Modified Membrane and PE or PVC 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 the one in the Blend rubber adhesive layer of PVC 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. PE according to claim 1 or PVC base decorating film, 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. PE according to claim 1 and 2 or PVC base decorating film, 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. PE according to claim 3 or PVC base decorating film, is characterized in that: described barrier layer also comprises (with weight parts) modified PMMA 0 ~ 60 part.
5. PE according to claim 3 or PVC base decorating film, is characterized in that: described fluorine-containing polymer is one or both in PVDF, PTFE, PFA, PCTFE.
6. PE according to claim 1 and 2 or PVC base decorating film, is characterized in that: mainly consisting of (with weight parts) of described tack coat, random copolymer 80-100 part of nano modification copolyamide and ethene, PVDF0-20 part.
7. PE according to claim 1 and 2 or PVC base decorating film, is characterized in that: mainly consisting of (with weight parts) of described tack coat, modified PMMA 80 ~ 100 parts, PVDF0 ~ 20 part.
CN201510665152.8A 2015-10-15 2015-10-15 PE or PVC base material decoration film Pending CN105291499A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106626669A (en) * 2016-11-24 2017-05-10 浙江歌瑞新材料有限公司 High-weather-resistant and abrasion-resistant polyvinyl chloride floor
CN108587530A (en) * 2018-05-18 2018-09-28 杭州海维特化工科技有限公司 A kind of PVC furniture film/PVF plastic foil Aqueous Adhesives and preparation method thereof
CN114103339A (en) * 2021-10-27 2022-03-01 南通百晟新材料科技有限责任公司 Bending-resistant and impact-resistant steel plate water-based decorative film and preparation method thereof

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Publication number Priority date Publication date Assignee Title
US5256472A (en) * 1988-12-05 1993-10-26 Denki Kagaku Kogyo Kabushiki Kaisha Fluorine resin type weather-resistant film
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
CN101410249A (en) * 2006-01-25 2009-04-15 阿克马法国公司 Flexible film based on fluorinated polymer
CN101879808A (en) * 2010-06-22 2010-11-10 李民 Method for bonding fluoroplastic layer and polyester layer

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US5256472A (en) * 1988-12-05 1993-10-26 Denki Kagaku Kogyo Kabushiki Kaisha Fluorine resin type weather-resistant film
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
CN101410249A (en) * 2006-01-25 2009-04-15 阿克马法国公司 Flexible film based on fluorinated polymer
CN101879808A (en) * 2010-06-22 2010-11-10 李民 Method for bonding fluoroplastic layer and polyester layer

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106626669A (en) * 2016-11-24 2017-05-10 浙江歌瑞新材料有限公司 High-weather-resistant and abrasion-resistant polyvinyl chloride floor
CN108587530A (en) * 2018-05-18 2018-09-28 杭州海维特化工科技有限公司 A kind of PVC furniture film/PVF plastic foil Aqueous Adhesives and preparation method thereof
CN108587530B (en) * 2018-05-18 2020-02-21 杭州海维特化工科技有限公司 PVC furniture film/PVF plastic film aqueous adhesive and preparation method thereof
CN114103339A (en) * 2021-10-27 2022-03-01 南通百晟新材料科技有限责任公司 Bending-resistant and impact-resistant steel plate water-based decorative film and preparation method thereof

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Application publication date: 20160203