CN105061793A - Skin-protection automobile film and preparation method thereof - Google Patents
Skin-protection automobile film and preparation method thereof Download PDFInfo
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- CN105061793A CN105061793A CN201510502247.8A CN201510502247A CN105061793A CN 105061793 A CN105061793 A CN 105061793A CN 201510502247 A CN201510502247 A CN 201510502247A CN 105061793 A CN105061793 A CN 105061793A
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Abstract
The invention discloses a skin-protection automobile film and a preparation method thereof. The skin-protection automobile film comprises a release substrate layer, a high-temperature-resistant layer, an abrasion-resistant layer, a thermal insulation layer and a uvioresistant layer, wherein the outer surface of the release substrate layer is coated with the high-temperature-resistant layer; the surface of the high-temperature-resistant layer is coated with the abrasion-resistant layer; the inner surface of the release substrate layer is coated with the thermal insulation layer; the surface of the thermal insulation layer is coated with the uvioresistant layer; the uvioresistant layer is mainly composed of polyimide, a plasticizer, a thermoplastic polyester elastomer and a uvioresistant nano-composite.
Description
Technical field
The present invention relates to automobile adhesive film field, specifically, is automobile adhesive film of a kind of uvioresistant skin care and preparation method thereof.
Background technology
Along with climbing up and up of automobile usage quantity, increasing people becomes car owners.No matter be working or tourism, often all can select to go on a journey by bus, automobile belt gives us conveniently simultaneously, and also the skin of exempt from customs examination people does not cause ultraviolet injury.
Ultraviolet refers to one section in the 10 ~ 400nm wavelength region in electromagnetic spectrum, is found by roentgen in 1802.Effects different is separately shown due to the beam wavelength change in this wavelength region, for investigation and application is convenient, International Commission on Illumination is divided into UVA (320-400nm), UVB (280-320nm), UVC (200-280nm) three wave bands ultraviolet.The ultraviolet that wavelength is less than 200nm due to consumingly absorb by air (mainly oxygen) wherein, so be only suitable for studying in vacuum environment, therefore be often called as vacuum ultraviolet ray or be called as extreme ultraviolet.Ultraviolet accounts for 5% in daylight, wherein the large percentage of UVA, and UVB ratio is less, and the destruction of UVB is 1000 times of UVA.UVA is also called long wave blackspot effect ultraviolet, there is very strong penetrativity, the transparent glass of major part and plastics can be penetrated, and the long wave ultraviolet contained in daylight has and to penetrate ozonosphere more than 98% and cloud layer arrives earth surface, UVA can go directly the skin corium of skin, destroy spandex fiber and collagen fabric, by our skin tanning.UVB is also called medium wave erythemal effect ultraviolet, there is the problem causing skin carcinoma, erythema aestivum is mainly due to the effect of UVB, veins beneath the skin can cause expansion after absorbing ultraviolet (UV) B, make erythrosis, produce erythema, be inflamed time serious, it equally also can have influence on subcutaneous elastic cell, skin is followed the string, forms coarse wrinkle.UVC, as a kind of stronger ultraviolet, has certain germicidal action, but also harmful.UVC is shorter due to wavelength, is absorbed in atmosphere, can not reach the surface of the earth, but due to the increase of oxygen level in air in recent years, the increase of Ozone hole, UVB and UVC reaching ground also increases thereupon.
Automobile in the process of moving, vehicle glass can not hinder ultraviolet penetrating completely, human body keeps the state of sitting quietly substantially, in the course of time, or human body skin can be tanned severely, in order to reduce the ultraviolet damage of skin in automobile, need to take adequate measures to reduce ultraviolet through vehicle glass.
Summary of the invention
Main purpose of the present invention is to provide a kind of skin care automobile adhesive film and preparation method thereof, and it, by multi-functional rete, is achieved heat insulation, the uvioresistant at vehicle glass place, thus protection skin is from ultraviolet infringement.
For reaching above object, the technical solution used in the present invention is: a kind of skin care automobile adhesive film comprises release base layer; High-temperature-resistant layer, described high-temperature-resistant layer coats the outside surface of described release base layer; Wearing layer, described wearing layer coats described high-temperature-resistant layer surface; Thermofin, described thermofin coats the internal surface of described release base layer; And uvioresistant layer, described uvioresistant layer coats described thermofin surface, and wherein, described uvioresistant layer forms primarily of polyimide, softening agent, thermoplastic polyester elastomer and uvioresistant nano-complex.
According to one embodiment of the invention, described skin care automobile adhesive film comprises protective film further and installs glue-line, and described protective film is adhered to described uvioresistant layer surface separably by described installation glue-line.
According to one embodiment of the invention, described release base layer is primarily of polyimide, trifluoro propyl methyl cyclotrisiloxane, propylene glycol ester terephthalate, ethylene-vinyl acetate copolymer and vinyl silicone oil composition, wherein, the material composition composition of described release base layer is counted by weight: polyimide is 60 ~ 80 parts; Trifluoro propyl methyl cyclotrisiloxane is 10 ~ 30 parts; Propylene glycol ester terephthalate is 5 ~ 25 parts; Ethylene-vinyl acetate copolymer is 2 ~ 10 parts; Vinyl silicone oil is 2 ~ 8 parts; Diethylene glycol dibenzoate is 2 ~ 10 parts; And oxidation inhibitor is 1 ~ 4 part.
According to one embodiment of the invention, the material composition composition of described uvioresistant layer is counted by weight: 50 ~ 60 parts of polyimide, 8 ~ 15 parts of softening agent, 8 ~ 12 parts of thermoplastic polyester elastomers, 2 ~ 3 parts of vinyltriisopropenyloxysilanes, the uvioresistant nano-complex of 10 ~ 15 parts, 2 ~ 4 parts of antioxidants.
According to one embodiment of the invention, described uvioresistant nano-complex is modification cladding nanometer titanium dioxide/cerium dioxide matrix material.
According to one embodiment of the invention, described thermofin is made up of nano titanium oxide, nano silicon and silicone resin; Described high-temperature-resistant layer is primarily of polyvinylidene fluoride polymer (PVDF) and additive composition; And described wearing layer is made up of silicon-dioxide and epoxy resin.
A preparation method for skin care automobile adhesive film, it comprises step:
S100 provides release base layer, and wherein, described release base layer is primarily of polyimide, trifluoro propyl methyl cyclotrisiloxane, propylene glycol ester terephthalate, ethylene-vinyl acetate copolymer and vinyl silicone oil composition;
Polyvinylidene fluoride polymer and additive-coated in described release base layer outside surface, are formed high-temperature-resistant layer by S200;
Silicon-dioxide and epoxy resin are coated described high-temperature-resistant layer surface by S300 successively, form wearing layer;
The silicone resin being dispersed with nano titanium oxide and nano silicon is coated the internal surface of described release base layer by S400, forms thermofin; And
Ultraviolet ray-resistant material is coated described thermofin surface by S500, form uvioresistant layer, wherein, described uvioresistant layer forms primarily of polyimide, softening agent, thermoplastic polyester elastomer and uvioresistant nano-complex, wherein, the material composition composition of described uvioresistant layer is counted by weight: 50 ~ 60 parts of polyimide, 8 ~ 15 parts of softening agent, 8 ~ 12 parts of thermoplastic polyester elastomers, 2 ~ 3 parts of vinyltriisopropenyloxysilanes, the uvioresistant nano composite material of 10 ~ 15 parts, 2 ~ 4 parts of antioxidants.
According to one embodiment of the invention, the preparation method of described skin care automobile adhesive film comprises step S600 further: by installing glue, polyethylene terephthalate being adhered to described uvioresistant layer separably, forming protective film.
Wherein, described step S100 comprises step:
Polyimide, trifluoro propyl methyl cyclotrisiloxane, Poly(Trimethylene Terephthalate), ethylene-vinyl acetate copolymer mix by preset weight part by S110, stir;
S120 adds the vinyl silicone oil of corresponding weight part, diethylene glycol dibenzoate, oxidation inhibitor stir, stirring velocity is 800-1000 rev/min, be heated to 140-160 DEG C simultaneously, obtain membrane coating material, wherein, the material composition composition of described membrane coating material is by weight: polyimide is 60 ~ 80 parts; Trifluoro propyl methyl cyclotrisiloxane is 10 ~ 30 parts; Propylene glycol ester terephthalate is 5 ~ 25 parts; Ethylene-vinyl acetate copolymer is 2 ~ 10 parts; Vinyl silicone oil is 2 ~ 8 parts; Diethylene glycol dibenzoate is 2 ~ 10 parts; And oxidation inhibitor is 1 ~ 4 part; And
Membrane coating material is passed through film machine film coextrusion head on polyethylene terephthalate base material by S130, and wherein, co-extrusion temperature is 230-260 DEG C, back pressure 600pa-1000pa, and co-extrusion speed is 100-150m/min, obtained described release base layer.
According to one embodiment of the invention, described step S500 comprises step:
S510 by nano-titanium dioxide coated nano cerium dioxide, obtains nano titanium oxide/cerium dioxide matrix material by sol-gel method;
Cladding nanometer titanium dioxide/cerium dioxide is scattered in ethanol mixed aqueous solution by S520, adds low-molecular polypropylene acid sodium dispersion agent; And
S530 dropwise drips titanate coupling agent wherein, carries out modification to described nano titanium oxide/cerium dioxide matrix material, makes a certain amount of vinylformic acid unsaturated group of described nano composite material surface grafting, obtains described uvioresistant nano composite material.
According to one embodiment of the invention, described step S500 comprises step further:
The nano titanium oxide of 5 ~ 10 mass parts is distributed in the dehydrated alcohol of 200 mass parts;
Add the Cerium II Chloride of 10 ~ 15 mass parts, stir after 5 ~ 10 minutes, dropwise added wherein by the methyl ethyl diketone of 3 ~ 5 mass parts, Room-temperature seal stirs 1 ~ 2 hour, and ageing is placed 2 ~ 3 hours, obtained nano titanium oxide/cerium dioxide mixed solution;
By centrifugal for nano titanium oxide/cerium dioxide mixed solution, repeatedly add 1,2 propylene glycol and ethanol purge, dry, obtain cladding nanometer titanium dioxide/cerium dioxide matrix material;
Described nano titanium oxide/cerium dioxide matrix material is scattered in the mixing solutions of ethanol and water, add the low-molecular polypropylene acid sodium of 5 ~ 15 mass parts, dropwise drip the titanate coupling agent of 3 ~ 6 mass parts wherein, abundant stirring after 5 ~ 10 minutes by the pH regulator to 9 of solution ~ 10, ultrasonic 3 ~ 5 minutes, continue stirring reaction 30 ~ 40 minutes, centrifugal, drying, obtains described uvioresistant nano-complex.
Beneficial effect of the present invention is: by using polyimide as the base layer chief component of automobile adhesive film, be conducive to the high thermal resistance and the wearing quality that improve automobile adhesive film; By adding homemade improvement cladding nanometer titanium dioxide/cerium dioxide matrix material in described uvioresistant layer, strengthen ultraviolet receptivity, the skin of protection occupant is from ultraviolet injury.
Accompanying drawing explanation
Fig. 1 is the structural representation of skin care automobile adhesive film according to a preferred embodiment of the present invention.
Description of reference numerals
1 skin care automobile adhesive film 10 release base layer 20 high-temperature-resistant layer 30 wearing layer
40 thermofin 50 uvioresistant layers 60 install glue-line 70 protective film
Embodiment
Below describe and realize the present invention for disclosing the present invention to enable those skilled in the art.Preferred embodiment in below describing only as an example, it may occur to persons skilled in the art that other apparent modification.
A kind of skin care automobile adhesive film 1 as shown in Figure 1, described skin care automobile adhesive film 1 comprises release base layer 10; High-temperature-resistant layer 20, described high-temperature-resistant layer 20 coats the outside surface of described release base layer 10; Wearing layer 30, described wearing layer 30 coats described high-temperature-resistant layer 20 surface; Thermofin 40, described thermofin 40 coats the internal surface of described release base layer 10; And uvioresistant layer 50, described uvioresistant layer 50 coats described thermofin 40 surface, and wherein, described uvioresistant layer 50 forms primarily of polyimide, softening agent, thermoplastic polyester elastomer and uvioresistant nano-complex.Thus by multi-functional rete, be achieved heat insulation, the uvioresistant at vehicle glass place, protection skin is from ultraviolet infringement.
Wherein, described skin care automobile adhesive film 1 comprises protective film 70 further and installs glue-line 60, and described protective film 70 is adhered to described uvioresistant layer 50 surface separably by described installation glue-line 60, is arranged at the internal layer of described automobile adhesive film 1.Wherein, described protective film 70 is polyethylene terephthalate layer (pet layers), and described installation glue-line 60 is silicone based adhesive-layers.
That is, described skin care automobile adhesive film 1 is followed successively by protective film 70 from inside to outside, installs glue-line 60, uvioresistant layer 50, thermofin 40, release base layer 10, high-temperature-resistant layer 20 and wearing layer 30.When described pad pasting is affixed on glass outer surface, remove described protective film 70, be affixed on vehicle glass outside surface by described uvioresistant layer 50.
Wherein, described release base layer 10 is primarily of polyimide, trifluoro propyl methyl cyclotrisiloxane, propylene glycol ester terephthalate, ethylene-vinyl acetate copolymer and vinyl silicone oil composition.
Wherein, because polyimide (PI) can carry out work under condition for a long time more than 50 DEG C, short-term job temperature can reach 450 DEG C, that in current engineering plastics, high thermal resistance is best, made described release base layer 10 comparatively stable, can not be exposed to the sun and to be out of shape or character changes by Yin Gaowen, being suitable for the matrix as described skin care automobile adhesive film 1.
Wherein, trifluoro propyl methyl cyclotrisiloxane is the siloxanes of fluoro, main containing Si-O key in siloxane molecule, bond energy is 462KJ/mol, and the bond energy of C-O is 369KJ/mol, the bond energy of Si-O is larger than C-O, so siloxanes has thermotolerance preferably, in addition, large than C-O key of Si-O bond angle, and Siliciumatom is larger than carbon atom, methyl occupies suitable space when rotating around Si-O key, and intermolecular gravitation is diminished, between siloxane molecule, gravitation is little, illustrate that its internal cohesive energy is little, resistance to bond and the internal cohesive energy of polymer are closely related, and the material of fluorine silicon has superior thermotolerance, weathering resistance, and fluorine-containing compound has waterproof, oil resistant and solvent resistant, the advantages such as low surface energy, the release film of preparation can be made to have better resistance to elevated temperatures.
Wherein, because a lot of performances of described Poly(Trimethylene Terephthalate) (PTT) are between PET and PBT, ptt fiber combines flexibility, the fluffiness of acrylic fibers, the pollution resistance of terylene of nylon, add elasticity inherently, and can the feature such as normal temperature dyeing, the crushing resistance being conducive to described release matrix gets a promotion.Wherein, described vinyl silicone oil is linking agent.
Wherein, described ethylene-vinyl acetate copolymer (EVA) is nontoxic, tasteless, and grease resistance, acid and alkali corrosion have higher elasticity and toughness, low temperature performance excellent, also can play the effect of expanding material.Adding of EVA makes reactive grafting rate greatly improve, and mechanical property is greatly improved.EVA and polyimide, trifluoro propyl methyl cyclotrisiloxane and Poly(Trimethylene Terephthalate) have good consistency, obtain a kind of stable structure system, and in addition, EVA also can improve the toughness of material, make described skin care automobile adhesive film 1 more durable.
Described release base layer 10 also comprises softening agent and oxidation inhibitor, and wherein, described softening agent is diethylene glycol dibenzoate, and wherein, described oxidation inhibitor is antioxidant 1076.
Preferably, the composition of raw materials of the membrane coating material of described release base layer 10, its material composition composition is counted by weight: polyimide is 60 ~ 80 parts; Trifluoro propyl methyl cyclotrisiloxane is 10 ~ 30 parts; Propylene glycol ester terephthalate is 5 ~ 25 parts; Ethylene-vinyl acetate copolymer is 2 ~ 10 parts; Vinyl silicone oil is 2 ~ 8 parts; Diethylene glycol dibenzoate is 2 ~ 10 parts; And oxidation inhibitor is 1 ~ 4 part.
Wherein, the material composition composition of described uvioresistant layer 50 is counted by weight: 50 ~ 60 parts of polyimide, 8 ~ 15 parts of softening agent, 8 ~ 12 parts of thermoplastic polyester elastomers, 2 ~ 3 parts of vinyltriisopropenyloxysilanes, the uvioresistant nano composite material of 10 ~ 15 parts, 2 ~ 4 parts of antioxidants.
Wherein, described uvioresistant nano-complex is made primarily of titanium dioxide, cerium dioxide, low-molecular polypropylene acid sodium and titanate coupling agent.By sol-gel method by nanometer titanium dioxide-coated one deck nano ceric oxide, obtain titanium dioxide/ceria composites, again described titanium dioxide/ceria composites is added titanate coupling agent in low-molecular polypropylene acid sodium the solution of dispersion agent and carry out modification, obtain modification cladding nanometer titanium dioxide/cerium dioxide matrix material, prepare the described uvioresistant nano-complex of modification.
Because the 4f electronic structure of cerium dioxide has very strong ultraviolet absorption ability, and to visible ray without characteristic absorbance, cerium dioxide size is less than light wave, visible ray be can pass through, have stronger reflection or scattering process to UV-light, therefore nano ceric oxide has absorption to ultraviolet and shields bifunctional effect.Meanwhile, due to Ti in titanium dioxide
4+3d rail mounted complete empty, do not have electronics to participate in transition, ion itself also can strong absorption ultraviolet.
Wherein, described titanium dioxide/ceria composites is through titanate coupling agent modified, its surface has undersaturated group, and can at a certain amount of vinylformic acid of surface grafting, described uvioresistant nano-complex is dispersed in described uvioresistant layer 50 better, and in described thin film system, is able to there is consistency preferably with other component.
Wherein, described thermofin 40 is made up of nano titanium oxide, nano silicon and silicone resin, obtained by nano titanium oxide and nano silicon being dispersed in described silicone resin, described thermofin 40 is effectively ended near infrared light, reduces thermal radiation.
Wherein, described high-temperature-resistant layer 20 is primarily of polyvinylidene fluoride polymer (PVDF) and additive composition, and wherein, described additive comprises dispersion agent, antioxidant and nano aluminium oxide.
Wherein, described wearing layer 30 is made up of silicon-dioxide and epoxy resin, by silica-coating in described high-temperature-resistant layer 20 surface, after Air drying, form silica coating, epoxy resin is coated described silica coating surface, be placed in dustfree environment, place at 150 ~ 160 DEG C and carry out solidifying film layer in 2 ~ 3 hours.
A preparation method for skin care automobile adhesive film 1, it comprises step:
S100 provides release base layer 10, and wherein, described release base layer 10 is primarily of polyimide, trifluoro propyl methyl cyclotrisiloxane, propylene glycol ester terephthalate, ethylene-vinyl acetate copolymer and vinyl silicone oil composition;
Polyvinylidene fluoride polymer and additive-coated in described release base layer 10 outside surface, are formed high-temperature-resistant layer 20 by S200;
Silicon-dioxide and epoxy resin are coated described high-temperature-resistant layer 20 surface by S300 successively, form wearing layer 30;
The silicone resin being dispersed with nano titanium oxide and nano silicon is coated the internal surface of described release base layer 10 by S400, forms thermofin 40; And
Ultraviolet ray-resistant material is coated described thermofin 40 surface by S500, form uvioresistant layer 50, wherein, described uvioresistant layer 50 forms primarily of polyimide, softening agent, thermoplastic polyester elastomer and uvioresistant nano-complex, wherein, the material composition composition of described uvioresistant layer 50 is counted by weight: 50 ~ 60 parts of polyimide, 8 ~ 15 parts of softening agent, 8 ~ 12 parts of thermoplastic polyester elastomers, 2 ~ 3 parts of vinyltriisopropenyloxysilanes, the uvioresistant nano composite material of 10 ~ 15 parts, 2 ~ 4 parts of antioxidants.
Wherein, the preparation method of described skin care automobile adhesive film 1 comprises step S600 further: by installing glue, polyethylene terephthalate being adhered to described uvioresistant layer 50 separably, forming protective film 70.
Wherein, described step S100 comprises step:
Polyimide, trifluoro propyl methyl cyclotrisiloxane, Poly(Trimethylene Terephthalate), ethylene-vinyl acetate copolymer mix by preset weight part by S110, stir;
S120 adds the vinyl silicone oil of corresponding weight part, diethylene glycol dibenzoate, oxidation inhibitor stir, stirring velocity is 800-1000 rev/min, be heated to 140-160 DEG C simultaneously, obtain membrane coating material, wherein, the material composition composition of described membrane coating material is by weight: polyimide is 60 ~ 80 parts; Trifluoro propyl methyl cyclotrisiloxane is 10 ~ 30 parts; Propylene glycol ester terephthalate is 5 ~ 25 parts; Ethylene-vinyl acetate copolymer is 2 ~ 10 parts; Vinyl silicone oil is 2 ~ 8 parts; Diethylene glycol dibenzoate is 2 ~ 10 parts; And oxidation inhibitor is 1 ~ 4 part; And
Membrane coating material is passed through film machine film coextrusion head on polyethylene terephthalate base material by S130, and wherein, co-extrusion temperature is 230-260 DEG C, back pressure 600pa-1000pa, and co-extrusion speed is 100-150m/min, obtained described release base layer 10.
Wherein, described step S500 comprises step:
S510 by nano-titanium dioxide coated nano cerium dioxide, obtains nano titanium oxide/cerium dioxide matrix material by sol-gel method;
Cladding nanometer titanium dioxide/cerium dioxide is scattered in ethanol mixed aqueous solution by S520, adds low-molecular polypropylene acid sodium dispersion agent; And
S530 dropwise drips titanate coupling agent wherein, carries out modification to described nano titanium oxide/cerium dioxide matrix material, makes a certain amount of vinylformic acid unsaturated group of described nano composite material surface grafting, obtains described uvioresistant nano composite material.
Wherein, described step S500 comprises step further:
The nano titanium oxide of 5 ~ 10 mass parts is distributed in the dehydrated alcohol of 200 mass parts;
Add the Cerium II Chloride of 10 ~ 15 mass parts, stir after 5 ~ 10 minutes, dropwise added wherein by the methyl ethyl diketone of 3 ~ 5 mass parts, Room-temperature seal stirs 1 ~ 2 hour, and ageing is placed 2 ~ 3 hours, obtained nano titanium oxide/cerium dioxide mixed solution;
By centrifugal for nano titanium oxide/cerium dioxide mixed solution, repeatedly add 1,2 propylene glycol and ethanol purge, dry, obtain cladding nanometer titanium dioxide/cerium dioxide matrix material;
Described nano titanium oxide/cerium dioxide matrix material is scattered in the mixing solutions of ethanol and water, add the low-molecular polypropylene acid sodium of 5 ~ 15 mass parts, dropwise drip the titanate coupling agent of 3 ~ 6 mass parts wherein, abundant stirring after 5 ~ 10 minutes by the pH regulator to 9 of solution ~ 10, ultrasonic 3 ~ 5 minutes, continue stirring reaction 30 ~ 40 minutes, centrifugal, drying, obtains described uvioresistant nano-complex.
Embodiment one
Described step S100 comprises step:
Polyimide, trifluoro propyl methyl cyclotrisiloxane, Poly(Trimethylene Terephthalate), ethylene-vinyl acetate copolymer mix by preset weight part by S110, stir;
S120 adds the vinyl silicone oil of corresponding weight part, diethylene glycol dibenzoate, oxidation inhibitor stir, stirring velocity is 800 revs/min, is heated to 150 DEG C simultaneously, obtains membrane coating material, wherein, the material composition composition of described membrane coating material is by weight: polyimide is 70 parts; Trifluoro propyl methyl cyclotrisiloxane is 20 parts; Propylene glycol ester terephthalate is 15 parts; Ethylene-vinyl acetate copolymer is 5 parts; Vinyl silicone oil is 5 parts; Diethylene glycol dibenzoate is 6 parts; And oxidation inhibitor is 2 parts; And
Membrane coating material is passed through film machine film coextrusion head in PET base material by S130, and wherein, co-extrusion temperature is 250 DEG C, back pressure 800pa, and co-extrusion speed is 150m/min, obtained described release base layer 10.
The material composition composition of described uvioresistant layer 50 is counted by weight: 60 parts of polyimide, 8 parts of softening agent, 8 parts of thermoplastic polyester elastomers, 3 parts of vinyltriisopropenyloxysilanes, the uvioresistant nano composite material of 13 parts, 3 parts of antioxidants.
Described step S500 comprises step further:
The nano titanium oxide of 6 mass parts is distributed in the dehydrated alcohol of 200 mass parts;
Add the Cerium II Chloride of 12 mass parts, stir after 6 minutes, dropwise added wherein by the methyl ethyl diketone of 4 mass parts, Room-temperature seal stirs 1 hour, and ageing places 2 hours, obtained nano titanium oxide/cerium dioxide mixed solution;
By centrifugal for nano titanium oxide/cerium dioxide mixed solution, repeatedly add 1,2 propylene glycol and ethanol purge, dry, obtain cladding nanometer titanium dioxide/cerium dioxide matrix material;
Described nano titanium oxide/cerium dioxide matrix material is scattered in the mixing solutions of ethanol and water, add the low-molecular polypropylene acid sodium of 15 mass parts, dropwise drip the titanate coupling agent of 3 mass parts wherein, abundant stirring after 8 minutes by the pH regulator to 9 of solution ~ 10, ultrasonic 4 minutes, continue stirring reaction 30 minutes, centrifugal, drying, obtains described uvioresistant nano-complex.
Embodiment two
Described step S100 comprises step:
Polyimide, trifluoro propyl methyl cyclotrisiloxane, Poly(Trimethylene Terephthalate), ethylene-vinyl acetate copolymer mix by preset weight part by S110, stir;
S120 adds the vinyl silicone oil of corresponding weight part, diethylene glycol dibenzoate, oxidation inhibitor stir, stirring velocity is 1000 revs/min, is heated to 160 DEG C simultaneously, obtains membrane coating material, wherein, the material composition composition of described membrane coating material is by weight: polyimide is 80 parts; Trifluoro propyl methyl cyclotrisiloxane is 20 parts; Propylene glycol ester terephthalate is 20 parts; Ethylene-vinyl acetate copolymer is 8 parts; Vinyl silicone oil is 6 parts; Diethylene glycol dibenzoate is 4 parts; And oxidation inhibitor is 1 part; And
Membrane coating material is passed through film machine film coextrusion head in PET base material by S130, and wherein, co-extrusion temperature is 260 DEG C, back pressure 1000pa, and co-extrusion speed is 150m/min, obtained described release base layer 10.
The material composition composition of described uvioresistant layer 50 is counted by weight: 50 parts of polyimide, 12 parts of softening agent, 10 parts of thermoplastic polyester elastomers, 3 parts of vinyltriisopropenyloxysilanes, the uvioresistant nano composite material of 10 parts, 4 parts of antioxidants.
Described step S500 comprises step further:
The nano titanium oxide of 8 mass parts is distributed in the dehydrated alcohol of 200 mass parts;
Add the Cerium II Chloride of 10 mass parts, stir after 6 minutes, dropwise added wherein by the methyl ethyl diketone of 4 mass parts, Room-temperature seal stirs 1 hour, and ageing places 2 hours, obtained nano titanium oxide/cerium dioxide mixed solution;
By centrifugal for nano titanium oxide/cerium dioxide mixed solution, repeatedly add 1,2 propylene glycol and ethanol purge, dry, obtain cladding nanometer titanium dioxide/cerium dioxide matrix material;
Described nano titanium oxide/cerium dioxide matrix material is scattered in the mixing solutions of ethanol and water, add the low-molecular polypropylene acid sodium of 12 mass parts, dropwise drip the titanate coupling agent of 5 mass parts wherein, abundant stirring after 5 minutes by the pH regulator to 9 of solution ~ 10, ultrasonic 4 minutes, continue stirring reaction 30 minutes, centrifugal, drying, obtains described uvioresistant nano-complex.
Embodiment three
Described step S100 comprises step:
Polyimide, trifluoro propyl methyl cyclotrisiloxane, Poly(Trimethylene Terephthalate), ethylene-vinyl acetate copolymer mix by preset weight part by S110, stir;
S120 adds the vinyl silicone oil of corresponding weight part, diethylene glycol dibenzoate, oxidation inhibitor stir, stirring velocity is 1000 revs/min, is heated to 160 DEG C simultaneously, obtains membrane coating material, wherein, the material composition composition of described membrane coating material is by weight: polyimide is 80 parts; Trifluoro propyl methyl cyclotrisiloxane is 10 parts; Propylene glycol ester terephthalate is 25 parts; Ethylene-vinyl acetate copolymer is 7 parts; Vinyl silicone oil is 5 parts; Diethylene glycol dibenzoate is 10 parts; And oxidation inhibitor is 2 parts; And
Membrane coating material is passed through film machine film coextrusion head in PET base material by S130, and wherein, co-extrusion temperature is 230 DEG C, back pressure 600pa, and co-extrusion speed is 100m/min, obtains described release base layer 10.
The material composition composition of described uvioresistant layer 50 is counted by weight: 55 parts of polyimide, 14 parts of softening agent, 12 parts of thermoplastic polyester elastomers, 2 parts of vinyltriisopropenyloxysilanes, the uvioresistant nano composite material of 14 parts, 2 parts of antioxidants.
Described step S500 comprises step further:
The nano titanium oxide of 9 mass parts is distributed in the dehydrated alcohol of 200 mass parts;
Add the Cerium II Chloride of 14 mass parts, stir after 10 minutes, dropwise added wherein by the methyl ethyl diketone of 5 mass parts, Room-temperature seal stirs 1 hour, and ageing places 2 hours, obtained nano titanium oxide/cerium dioxide mixed solution;
By centrifugal for nano titanium oxide/cerium dioxide mixed solution, repeatedly add 1,2 propylene glycol and ethanol purge, dry, obtain cladding nanometer titanium dioxide/cerium dioxide matrix material;
Described nano titanium oxide/cerium dioxide matrix material is scattered in the mixing solutions of ethanol and water, add the low-molecular polypropylene acid sodium of 12 mass parts, dropwise drip the titanate coupling agent of 5 mass parts wherein, abundant stirring after 10 minutes by the pH regulator to 9 of solution ~ 10, ultrasonic 5 minutes, continue stirring reaction 40 minutes, centrifugal, drying, obtains described uvioresistant nano-complex.
Prepared the skin care automobile adhesive film 1 of different performance by the method in embodiment one to three, adopt following method to do corresponding performance test to different skin care automobile adhesive films 1.
1, the transparency test of film, adopt mist degree (Haze) and transmittance to represent, the condition of measurement performs according to GB/T2410-2008.
2, ultraviolet isolating rate test, adopts Japanese Shimadzu UV-3600 type spectrophotometer to test, and detects with reference to standard GB/T/T2680.
Performance detection data as in the table below
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; the just principle of the present invention described in above-described embodiment and specification sheets; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in claimed scope of the present invention.The protection domain of application claims is defined by appending claims and equivalent thereof.
Claims (10)
1. a skin care automobile adhesive film, is characterized in that, comprising:
Release base layer;
High-temperature-resistant layer, described high-temperature-resistant layer coats the outside surface of described release base layer;
Wearing layer, described wearing layer coats described high-temperature-resistant layer surface;
Thermofin, described thermofin coats the internal surface of described release base layer; And
Uvioresistant layer, described uvioresistant layer coats described thermofin surface, and wherein, described uvioresistant layer forms primarily of polyimide, softening agent, thermoplastic polyester elastomer and uvioresistant nano-complex.
2. skin care automobile adhesive film according to claim 1, is characterized in that, comprises protective film further and installs glue-line, and described protective film is adhered to described uvioresistant layer surface separably by described installation glue-line.
3. skin care automobile adhesive film according to claim 2, it is characterized in that, described release base layer is primarily of polyimide, trifluoro propyl methyl cyclotrisiloxane, propylene glycol ester terephthalate, ethylene-vinyl acetate copolymer and vinyl silicone oil composition, wherein, the material composition composition of described release base layer is counted by weight: polyimide is 60 ~ 80 parts; Trifluoro propyl methyl cyclotrisiloxane is 10 ~ 30 parts; Propylene glycol ester terephthalate is 5 ~ 25 parts; Ethylene-vinyl acetate copolymer is 2 ~ 10 parts; Vinyl silicone oil is 2 ~ 8 parts; Diethylene glycol dibenzoate is 2 ~ 10 parts; And oxidation inhibitor is 1 ~ 4 part.
4. skin care automobile adhesive film according to claim 3, it is characterized in that, the material composition composition of described uvioresistant layer is counted by weight: 50 ~ 60 parts of polyimide, 8 ~ 15 parts of softening agent, 8 ~ 12 parts of thermoplastic polyester elastomers, 2 ~ 3 parts of vinyltriisopropenyloxysilanes, the uvioresistant nano-complex of 10 ~ 15 parts, 2 ~ 4 parts of antioxidants.
5. skin care automobile adhesive film according to claim 4, is characterized in that, described uvioresistant nano-complex is modification cladding nanometer titanium dioxide/cerium dioxide matrix material.
6., according to described skin care automobile adhesive film arbitrary in claim 1 to 5, it is characterized in that, described thermofin is made up of nano titanium oxide, nano silicon and silicone resin; Described high-temperature-resistant layer is primarily of polyvinylidene fluoride polymer and additive composition; Described wearing layer is made up of silicon-dioxide and epoxy resin.
7. a preparation method for skin care automobile adhesive film, is characterized in that, comprises step:
S100 provides release base layer, and wherein, described release base layer is primarily of polyimide, trifluoro propyl methyl cyclotrisiloxane, propylene glycol ester terephthalate, ethylene-vinyl acetate copolymer and vinyl silicone oil composition;
Polyvinylidene fluoride polymer and additive-coated in described release base layer outside surface, are formed high-temperature-resistant layer by S200;
Silicon-dioxide and epoxy resin are coated described high-temperature-resistant layer surface by S300 successively, form wearing layer;
The silicone resin being dispersed with nano titanium oxide and nano silicon is coated the internal surface of described release base layer by S400, forms thermofin;
Ultraviolet ray-resistant material is coated described thermofin surface by S500, form uvioresistant layer, wherein, described uvioresistant layer forms primarily of polyimide, softening agent, thermoplastic polyester elastomer and uvioresistant nano-complex, wherein, the material composition composition of described uvioresistant layer is counted by weight: 50 ~ 60 parts of polyimide, 8 ~ 15 parts of softening agent, 8 ~ 12 parts of thermoplastic polyester elastomers, 2 ~ 3 parts of vinyltriisopropenyloxysilanes, the uvioresistant nano-complex of 10 ~ 15 parts, 2 ~ 4 parts of antioxidants; And
Polyethylene terephthalate is adhered to described uvioresistant layer by installing glue by S600 separably, forms protective film.
8. the preparation method of skin care automobile adhesive film according to claim 7, is characterized in that, described step S100 comprises step:
Polyimide, trifluoro propyl methyl cyclotrisiloxane, Poly(Trimethylene Terephthalate), ethylene-vinyl acetate copolymer mix by preset weight part by S110, stir;
S120 adds the vinyl silicone oil of corresponding weight part, diethylene glycol dibenzoate, oxidation inhibitor stir, stirring velocity is 800 ~ 1000 revs/min, be heated to 140-160 DEG C simultaneously, obtain membrane coating material, wherein, the material composition composition of described membrane coating material is by weight: polyimide is 60 ~ 80 parts; Trifluoro propyl methyl cyclotrisiloxane is 10 ~ 30 parts; Propylene glycol ester terephthalate is 5 ~ 25 parts; Ethylene-vinyl acetate copolymer is 2 ~ 10 parts; Vinyl silicone oil is 2 ~ 8 parts; Diethylene glycol dibenzoate is 2 ~ 10 parts; And oxidation inhibitor is 1 ~ 4 part; And
Membrane coating material is passed through film machine film coextrusion head on polyethylene terephthalate base material by S130, and wherein, co-extrusion temperature is 230-260 DEG C, back pressure 600pa-1000pa, and co-extrusion speed is 100-150m/min, obtained described release base layer.
9. the preparation method of skin care automobile adhesive film according to claim 8, is characterized in that, described step S500 comprises step:
S510 by nano-titanium dioxide coated nano cerium dioxide, obtains nano titanium oxide/cerium dioxide matrix material by sol-gel method;
Cladding nanometer titanium dioxide/cerium dioxide is scattered in ethanol mixed aqueous solution by S520, adds low-molecular polypropylene acid sodium dispersion agent; And
S530 dropwise drips titanate coupling agent wherein, carries out modification to described nano titanium oxide/cerium dioxide matrix material, makes a certain amount of vinylformic acid unsaturated group of described nano composite material surface grafting, obtains described uvioresistant nano composite material.
10. the preparation method of skin care automobile adhesive film according to claim 9, is characterized in that, described step S500 comprises step further:
The nano titanium oxide of 5 ~ 10 mass parts is distributed in the dehydrated alcohol of 200 mass parts;
Add the Cerium II Chloride of 10 ~ 15 mass parts, stir after 5 ~ 10 minutes, dropwise added wherein by the methyl ethyl diketone of 3 ~ 5 mass parts, Room-temperature seal stirs 1 ~ 2 hour, and ageing is placed 2 ~ 3 hours, obtained nano titanium oxide/cerium dioxide mixed solution;
By centrifugal for nano titanium oxide/cerium dioxide mixed solution, repeatedly add 1,2 propylene glycol and ethanol purge, dry, obtain cladding nanometer titanium dioxide/cerium dioxide matrix material; And
Described nano titanium oxide/cerium dioxide matrix material is scattered in the mixing solutions of ethanol and water, add the low-molecular polypropylene acid sodium of 5 ~ 15 mass parts, dropwise drip the titanate coupling agent of 3 ~ 6 mass parts wherein, abundant stirring after 5 ~ 10 minutes by the pH regulator to 9 of solution ~ 10, ultrasonic 3 ~ 5 minutes, continue stirring reaction 30 ~ 40 minutes, centrifugal, drying, obtains described uvioresistant nano-complex.
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| CN110264863A (en) * | 2019-07-13 | 2019-09-20 | 广州彩邦印刷有限公司 | Wear-resisting label |
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