JP2824796B2 - Fluororesin laminated film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides various properties such as weather resistance and stain resistance by forming a printed layer on the surface of a fluororesin film and imparting decorativeness and design. The present invention relates to a fluororesin laminated film which can be used as a marking film, a film for solar power, a release film, a film for electric insulation, a weather-resistant laminate film, and a film for weather-resistant metal laminate.

[Conventional technology]

Fluorine-based resin films are used as solar films because of their excellent weather resistance, heat resistance, chemical resistance, electrical properties, mechanical properties, and the like.

[Problems to be Solved by the Invention] However, it is generally difficult to color a fluororesin film, and it is possible to knead a coloring component such as a specific pigment into the fluororesin to color the whole in the same color. There is a problem that it is extremely difficult to print and color characters, figures, and the like for decoration, display, and the like on the surface of the film.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a fluororesin laminated film whose surface is strongly printed with characters, figures, coloring, etc., on which a fluororesin composition is printed.

[Means for solving the problem]

The present invention has achieved the above object by providing a fluororesin laminated film having a printed layer made of a fluororesin composition on at least one surface of the fluororesin film.

In the present invention, since the printing layer is composed of the fluororesin composition, characters, figures, coloring, etc. are printed firmly, and weather resistance, heat resistance, chemical resistance, electrical properties, mechanical properties, etc. A fluororesin laminated film having excellent is formed.

As the fluororesin constituting the fluororesin film, ethylene-tetrafluoroethylene-based copolymer, ethylene trifluoride copolymer, vinylidene fluoride copolymer, vinyl fluoride polymer, fluorinated alkoxyethylene resin, Examples thereof include a tetrafluoroethylene resin and a tetrafluoroethylene-propylene hexafluoride copolymer. Among them, an ethylene-tetrafluoroethylene copolymer is particularly preferable. Among them, a molar ratio of ethylene tetrafluoride / ethylene is preferable. There is 40 / 60-60 / 40, the formula _{CH 2 = CH-C n F} 2n + 1 ( where, n in the formula is 2
It is particularly preferable that the content of the perfluoroalkylvinyl monomer represented by the formula (10) is 0.1 to 10 mol% and the volume flow rate (melt flow index) is 10 to 500 mm ³ / sec. The above "volume flow rate" was measured at a predetermined temperature and a load of 30 kg / c using a descending flow tester.
under the m ^3, a nozzle system 1 mm, expressed a sample of 1g from the nozzle of the land 2mm extruded in a volume of molten sample is extruded in a unit time of the time, the predetermined temperature, melt molding of a sample resin A temperature in a possible temperature range (a temperature range between the flow start temperature and the thermal decomposition start temperature) and close to the flow start temperature is employed.

It is preferable that the ethylene-tetrafluoroethylene-based copolymer has the above-mentioned volume flow rate because a good fluorine-based resin film having high adhesion strength can be obtained.

Further, prior to printing the fluororesin composition on the fluororesin film, the surface of the fluororesin film is subjected to corona discharge treatment, plast treatment, sodium etching treatment, etc., and the surface tension is reduced to, for example, 35 dynes.
/ dyne / cm or more, particularly 38 dyne / cm or more, and more preferably 40 dyne / cm or more is preferable from the standpoint of enhancing adhesion. Among them, preferred methods include a corona discharge treatment and a chemical etching treatment with a sodium complex, which will be described in detail below.

As the corona discharge treatment, using a corona discharge treatment device (manufactured by Kasuga Electric Co., Ltd.) to which an insulating ceramic electrode is applied, for example, subjecting the treated surface to electric discharge machining under a condition of 120 W / m ² · min, Surface tension. At this time, if the non-printed surface is processed, problems such as a decrease in stain resistance may occur. Therefore, it is preferable to use a device with an improved electrode shape and an electrode moving device so that only a necessary portion can be processed. Also, avoiding unnecessary processing can be achieved by masking the non-printed surface with, for example, a polyethylene adhesive film.

As a chemical etching treatment using a sodium-complex, a sodium-naphthalene complex
Surface treatment with a tetrahydrofuran solution of SD (N) (manufactured by Kawaken Fine Chemical Co., Ltd.) can be mentioned.

Other applicable surface treatment methods include flame treatment (for example, using a butane gas torch and
Flame treatment for 2 seconds), chromic acid mixed solution treatment (for example, 70 ° C)
Chromic acid: water: sulfuric acid = 70: 12: 150 immersion for 15 minutes, then take out and wash with water), UV treatment (for example,
Using a 160W high-pressure mercury lamp and irradiating with ultraviolet light) and surface roughening treatment (for example, the surface is roughened by spraying 100 mesh alumina powder and applying a pneumatic blast with a pressure of 3 kg / cm ² ). And the like.

The surface tension of the fluororesin film after the surface treatment was measured as follows.

That is, using a wetting index reagent (manufactured by Wako Pure Chemical Industries), the wetting index of the indicator that can be applied without repelling the indicator was measured, and the surface tension of the fluororesin film was determined according to JIS K6768.

The ink used to form the printing layer is made of a fluororesin composition described in detail below.

The above-mentioned fluorine-based resin composition (ink) has a melt flow index of 10 to 500, preferably 20 to 400, more preferably 30 to 30 of its solid content (excluding the solvent component).
It is adjusted to 0, and is mainly composed of a resin, a solvent, a thixotropy-imparting agent, and a pigment or dye, to which other various additives are added as necessary. The melt flow index is calculated based on the fluororesin layer 2 described above.
Is measured in the same manner as in the case of the fluororesin constituting That is, the melt flow index is a predetermined temperature using a descending flow tester, a nozzle diameter of 1 m at a load of 30 kg / cm ^2.
m, when melt extruded 1g sample from land 2mm nozzle,
It is defined by the value (mm ² / sec) expressed by the volume of the molten sample extruded per unit time. A temperature close to is employed.

If the melt flow index is less than 10, there is a tendency that the adhesion to the metal plate at the stage of heat fusion described below decreases, which is not preferable.
This tends to be undesirable because printing of figures and the like is blurred.

The fluororesin composition preferably has a thixotropic index (TI value) of 15 to 8, particularly preferably 2 to 8.
7, more preferably 3-6, even more preferably 4-6
It is desirable to adjust to. The TI value is BH at a temperature of 25 ° C.
Using a No. 7 rotor with a viscometer, the number of rotations was 2 and
Ratio of viscosity N ₂ to N ₂₀ measured at 20 revolutions, ie, TI = N ₂ / N
_Indicated at ₂₀ .

Next, each component of the above-mentioned fluorometer resin composition will be described.

Examples of the resin include a fluorine-based resin obtained by polymerization of olefin containing fluorine. In the present invention, a resin having a fluorine content of generally 30% by weight or more, particularly 40% by weight or more is preferably used. Examples of such a fluorine-based resin include ethylene-tetrafluoroethylene-based copolymer, ethylene-chlorotrifluoroethylene-based copolymer, hexafluoropropylene-tetrafluoroethylene-based copolymer, and perfluoroalkyl vinyl ether-
Examples include a tetrafluoroethylene-based copolymer, polyvinylidene fluoride, and polyvinyl fluoride. Although any of these can be used in the present invention, in particular, ethylene-tetrafluoroethylene-based copolymer is preferable, and among them, fluoroolefin, cyclohexyl vinyl ether, alkyl vinyl ether and hydroxyalkyl vinyl ether are essential components. Fluorine copolymers are preferred. In particular, in the fluorine-based copolymer, the content of units based on fluoroolefin, cyclohexyl vinyl ether, alkyl vinyl ether, hydroxyalkyl vinyl ether and other comonomer is respectively
40 to 60 mol%, 5 to 45 mol%, 5 to 45 mol%, 3 to 15 mol% and 0 to 30 mol%, and an uncured state having an intrinsic viscosity measured at 30 ° C. in tetrahydrofuran of 0.1%. ~
It is preferably 2.0 dl / g. Further, in the above fluorocopolymer, the fluoroolefin is a perhaloolefin such as chlorotrifluoroethylene or tetrafluoroethylene, and the alkyl vinyl ether contains a linear or branched alkyl group having 2 to 8 carbon atoms. More preferably, the hydroxyalkyl vinyl ether is hydroxybutyl vinyl ether.

As the solvent, those having a boiling point of from 120 to 230 ° C. are used, and preferred specific examples thereof include the following.

Aliphatic hydrocarbons; mineral spirits aromatic hydrocarbons; xylene, solvent naphtha, tetralin, dipentene, toluene alcohols; cyclohexyl alcohol, 2-methylcyclohexyl alcohol esters; butyl acetate ketones; cyclohexanone, methylcyclohexanone, diacetone alcohol, Isophorone glycols: ethylene glycol, propylene glycol glycol ethers; methyl cellosolve (ethylene glycol monomethyl ether), cellosolve (ethylene glycol monoethyl ether), butyl cellosolve,
Carbitol glycol ether ester; cellosolve acetate, butylsulosolve acetate, carbitol acetate (diethylene glycol monoethyl ether acetate) amides: dimethylformamide, dimethylacetamide Also, as the thixotropic agent, colloidal silica (Aerosil 400), Examples include aluminum alcoholate, organic bentonite, aluminum chelate, barium sulfate, and the like.

In addition, the above-mentioned pigments or dyes include the following, and are appropriately selected and used from these depending on the purpose and application.

Examples of inorganic pigments include titanium oxide, carbon black, red iron oxide, iron black, navy blue, ultramarine, zinc white, graphite, chrome vermillion, cobalt blue, calcined green, zinc sulfide, bronze powder, aluminum powder, pearl pigment, and the like. ,
As organic pigments, insoluble azo azo lakes, quinacridone red, carmine red, watching red, condensed azo red, perylene red, anthraquinone, disazo orange, dinitroan phosphorus orange, acetron orange, disazo yellow, hansa yellow, acetone yellow, Chlorinated phthalocyanine, Brillian green lake, phthalocyanine, indazulene blue, dioxazine violet, methyl violet, fluorescent pigments, luminous pigments, etc., and as the extender, precipitated barium sulfate, calcium carbonate, alumina white, clay, etc. Is mentioned. As the dye, ordinary acid dyes, basic dyes, oil-soluble dyes, disperse dyes, and the like can be used. As the oil-soluble dyes, azo-based, triarylmethane-based, anthraquinone-based, and azine-based dyes can be used. preferable.

Further, as other additives, a gelling agent, a thickener,
Examples include antioxidants, defoamers, matting agents, ultraviolet absorbers, and light stabilizers.

In addition, a crosslinking agent or a curing catalyst can be added as necessary. Examples of the crosslinking agent include polyisocyanate,
Butylated melamine, aluminum chelate and the like can be used, and as a curing catalyst, dibutyltin laurate and the like can be used.

The resin composition (ink) according to the present invention is composed of each of the above-described components.
50 to 150 parts by weight of solvent, 2 to 10 parts by weight of thixotropy-imparting agent, 100 parts by weight, appropriate amount of pigment or dye (usually 10 to 400 parts by weight) depending on the purpose and application, and other additives And, if necessary, 10 to 25 parts by weight of a crosslinking agent or a curing catalyst. In addition, when each component is blended, the melt flow index of the obtained resin composition is
It is necessary to select each component and their blending amount so as to be 10 to 500.

The printing layer may be formed by any means capable of forming a thin film of the fluororesin composition in close contact with the fluororesin composition. However, an ink composed of the resin composition is printed on the fluororesin layer by screen printing. An example is shown.
Hereinafter, a specific method for forming a printing layer on a fluororesin film will be described.

As the fluororesin film, for example, a thickness of 5 to 1000
The screen used for screen printing is used as a thin film (dry printed layer) of the resin composition, in order to obtain a thickness of 1 to 100 μ, for example, an opening of 100 to 300 mesh. Preferably, a screen is used.

Thus, in order to obtain a printed layer of the resin-coated metal of the first embodiment by screen printing, the above-mentioned resin composition is applied to the fluororesin film treated as described above by using a screen as described above and by a conventional method. What is necessary is to print an object (ink). At this time, if the thixotropy index of the fluororesin composition is less than 15, there is a tendency to cause inconveniences such as poor plate cutting and stringing, and if it is more than 8, generation of screen mesh and self-leveling property. There is a tendency for inconveniences such as a decrease in image quality.

Further, as a typical application example of the laminated film of the present invention, when a printed layer is layered inward on the surface of a metal plate such as an aluminum plate or an iron plate, and then heated to 260 to 360 ° C. and thermally fused, the weather resistance is improved. It is possible to obtain a resin laminated metal having excellent properties and decorativeness.

In the resin-laminated metal, the ink for forming the print layer has a melt flow index of a solid material, preferably 10 to 500, because it is formed of a fluororesin composition. In this case, the printed pattern shape can be maintained sharply, and at the same time, the printed layer can be firmly thermally fused to the metal surface.

Therefore, letters, figures, etc. are displayed on the metal surface with a strong printing layer which is thermally fused to the metal surface and interposed between the surface and the resin layer, and the printing layer is protected from the outside. This makes it possible to produce a resin-coated metal that is hardly peeled off.

Further, the laminated film of the present invention can also be used as a marking film. For example, an adhesive layer is provided on one of the laminated films of the present invention, and the laminated film is attached to an adherend for use.

The adhesive layer is not particularly limited, but in order to maintain a stable adhesive force over a long period of time, an adhesive resin component having a glass transition temperature of −100 to + 50 ° C., which will be described in detail below, It is preferable to use an adhesive composition containing a material having an absorbing function and a material having a photooxidation preventing function.

The adhesive resin component constituting the adhesive composition needs to have a glass transition temperature of −100 to + 50 ° C.,
In particular, the temperature is preferably from -80 to -20 ° C. When the galacto transition temperature is lower than -100 ° C, it is not suitable because the cohesive strength is reduced, and when it exceeds + 50 ° C, the impact resistance is lowered, which is not suitable.

The adhesive resin component is not particularly limited as long as it is a synthetic resin that can be used as an adhesive or an adhesive.Acrylic, urethane-based, ethylene-vinyl acetate-based, and silicone-based synthetic resins can be used. Acrylic resins are preferred.

Specific examples of the monomer constituting the acrylic resin include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and 2-methylbutyl acrylate. And the like.

The acrylic resin has n- as a main monomer.
Butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, i-nonyl acrylate, acrylic acid, methacrylic acid, acryl amide, N-methylol acryl amide and the like as auxiliary monomers (functional groups) are copolymerized, and the weight ratio is 99. You can choose between / 1/70/30.

Further, as a specific example, butyl acrylate (BA)
-Mixing ratio of both in the case of acrylic acid (AA) copolymer: B
A / AA (weight ratio) is preferably from 99.1 / 0.1 to 70/30, and more preferably from 99.5 / 0.5 to 80/20.

Materials having an ultraviolet absorbing function applicable to the adhesive composition include various ultraviolet absorbers such as cyanoacrylate-based, benzotriazole-based, benzophenone-based, salicylic acid-based, or hydroquinone-based, as well as reactive UV absorbers and polymers. Or a UV-absorbing polymer obtained by polymerizing a reactive UV absorber and a monomer.

In the case of the above-mentioned ultraviolet absorber, a benzotriazole-based ultraviolet absorber is particularly preferable, and as the benzotriazole-based ultraviolet absorber, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole is preferable. , 2-
[2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,
5-di-t-amyl-2-hydroxyphenylbenzotriazole and the like can be mentioned.

Further, as the benzophenone-based ultraviolet absorber,
2-hydroxy-4-octoxybenzophenone, 2,4
-Dihydroxybenzophenone, 2-hydroxy-4-
Methoxy-2'-carboxybenzophenone can be mentioned.

Examples of the salicylic acid-based ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, resorcinol monobenzoate, and 4-tert-butylphenyl salicylate.

Examples of the cyanoacrylate-based ultraviolet absorber include ethyl-2-cyano-3,3-diphenylacrylate and 2-ethylhexyl-2-cyano-3,3-diphenylacrylate.

The material having the ultraviolet absorption function preferably has a maximum absorption wavelength of 340 to 353 nm as its properties, and 343
More preferably, it is at 346346 nm.

In addition, the compounding amount of the material having the ultraviolet absorbing function,
It depends on the type, and is not particularly limited, but is preferably 0.5 to 10 parts by weight based on 100 parts by weight of the adhesive resin component (solid content) in order to sufficiently exhibit the performance of the material. , 0.6 to 2.5.

Examples of the material having a photooxidation preventing function applicable to the present invention include a hindered amine-based or hindered phenol-based antioxidant, and among them, a hindered amine-based antioxidant is preferable.

The hindered amine-based antioxidant is not particularly limited, but one having a high molecular weight and having an N-substituted piperidinol nucleus can be mentioned as a preferred example.

The molecular weight of the hindered amine antioxidant is preferably from 400 to 10,000, more preferably from 500 to 5,000.

As a specific compound of the above hindered amine-based antioxidant, a high molecular ester which is an ester of butanetetracarboxylic acid and N-substituted peridinol can be mentioned, and specific examples thereof include MARK LA-63 (trade name). Preferred examples include Adeka Argus Co., Ltd.), MARK LA-62 (trade name, manufactured by Adeka Argus Co., Ltd.), and TINUVIN-622LD (trade name, manufactured by Nippon Ciba Geigy Co., Ltd.). By using such a high molecular weight hindered amine antioxidant, bleed out can be prevented, and as a result, performance can be maintained for a long period of time.

In addition, the compounding amount of the material having the photooxidation prevention function,
It depends on the type, and is not particularly limited, but is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the adhesive resin component (solid content) in order to sufficiently exhibit the performance of the material. , 0.3 to 3 parts by weight.

The above-mentioned adhesive composition, in addition to the above-mentioned essential components, may be appropriately blended with commonly used components, for example, a solvent such as ethyl acetate and ethyl acetoacetate, various pigments and dyes, a crosslinking agent, and a crosslinking accelerator. It goes without saying that you can do it.

Examples of the crosslinking agent include isocyanates, epoxies, melamines, and aluminum chelates. Examples of the accelerator include dibutyltin laurate.

Next, among the adhesive compositions described in detail above, preferred compositions are shown in Table 1 below.

In Table 1, the acrylic resin (main pressure-sensitive adhesive) has a solid content of a copolymer (adhesive resin component) having a composition of butyl acrylate / acrylic acid = 97/3 and a solid content of 34% by weight. T-320 is 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole: a maximum absorption wavelength of 343 m.
m (manufactured by Ciba-Geigy) T-328 is 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole (manufactured by Ciba-Geigy) T-234 is 2- [2- Hydroxy-3,5-bis (α,
α-dimethylbenzyl) phenyl] -2H-benzotriazole (manufactured by Ciba-Geigy) MARK LA-63 is a hindered amine antioxidant having a molecular weight of 2060 (manufactured by Adeka Argus Co., Ltd.) C-EH is hexamethylene diisocyanate (Nippon Polyurethane Industry Co., Ltd.) Next, the effects of the present invention will be clarified by the following experimental examples.

(Experimental example)

Ethylene-tetrafluoroethylene having a molar ratio of ethylene tetrafluoride / ethylene of 53/47, a flow start temperature of 280 ° C., a thermal decomposition start temperature of 350 ° C., and a volume flow rate of 90 mm ² / sec at 300 ° C. A 20-micron-thick nonporous transparent film formed from a polymer by a hot melt extrusion method is prepared.

Next, the transparent film was subjected to a surface treatment using a corona discharge device (manufactured by Kasuga Electric) under a treatment condition of a discharge power of 120 W / m ² · min., And the surface of the film was subjected to a wetting index.
Ink 1 (surface viscosity 570ps. TI value 5) prepared by the following ink preparation method
Was printed on the above-mentioned transparent film made of an ethylene-tetrafluoroethylene copolymer using a screen made of Tetron having a mesh size of 270 mesh. 12
By heating and drying for 10 minutes in a hot air circulating dryer at 0 ° C., the fluororesin layer has a thickness of 10 μm comprising a thin film of the ink.
A printing film (invention product 1) on which the printed layer was formed in close contact was obtained.

On the other hand, after sandblasting one side of a 1100 series rolled aluminum plate shown in JIS H-4000 having a thickness of 2.0 mm to an average depth of irregularities of 10 to 15 microns (surface roughness) and a period of irregularities of 10 to 20 microns, A surface other than the one surface is masked with a vinyl chloride resin, and the sand blast surface is subjected to an electric field etching process. This electrolytic etching treatment was performed using a 3% aqueous solution of NaCl at a temperature of 40 ° C., an electric field density of 4 amps / dm ^{2, and a} current of 35 coulombs / cm ² .

After the etched surface was washed with water and dried, the aluminum plate was preheated to 310 ° C., the transparent film was placed on the etched surface, pressed under a pressure of 20 kg / cm ² , and subsequently pressed at 315 ° C.
Heat treatment for 0 minutes and heat fusion to form a fluorine-based resin layer on the aluminum plate, and obtain a resin-coated metal (Reference Invention Product 1) in which the printed layer is laminated on the surface of a fluorine-based resin layer. Was.

Invention 2 and Reference Invention 2 and Comparative Product were prepared in the same manner as Invention 1 except that Ink 2 and an acryl-urethane ink were prepared by the following ink preparation methods.

The performance was evaluated for each of the above inventions 1 to 2, reference inventions 1 to 2 and comparative products, and the results are shown in Table 2 below.
The results are shown in Table 3.

(Ink Preparation Method)-Ink 1-A copolymer of tetrafluoroethylene, cyclohexyl vinyl ether, ethyl vinyl ether and hydroxybutyl vinyl ether was obtained by a conventional method. In this copolymer, the molar ratio of each component was 50: 18: 22: 10 (by nuclear magnetic resonance method), and the intrinsic viscosity of the copolymer at 30 ° C. in tetrahydrofuran was 0.4 dl / g. there were. 100 g of this copolymer was dissolved in 80 g of carbitol acetate and 20 g of toluene, 50 g of titanium acetate and 6 g of colloidal silica were added, and the mixture was sufficiently mixed by a three-roll mill to obtain an ink composition. This composition had a viscosity of 270 ps. And a TI value of 5.

-Ink 2- (PVdF ink) 100 g of polyvinylidene fluoride in dimethylacetamide 20
0 g was stirred and dissolved at 60 ° C. to obtain a polyvinylidene fluoride solution having a solid content of 33%. To this solution, 50 g of titanium oxide and 3 g of colloidal silica were added and sufficiently mixed by a three-roll mill to obtain an ink composition.

The viscosity of this composition was 300 ps. And the TI value was 4 (ink for Invention 2).

(Acrylic-urethane based ink) Styrene 34 parts by weight, n-butyl acrylate 38 parts by weight, 2-hydroxyethyl acrylate 23.4
Acrylic polyol copolymer (having a hydroxyl value of 50 and a number average molecular weight of 1,500 parts by weight, acrylic acid of 0.4 parts by weight)
0) and coronate HL were dissolved in xylene at a molar ratio of 1: 1.5, and 20% of titanium oxide was added to obtain an ink (ink for comparison product).

In Table 3, the Taber abrasion, weather resistance and bending workability are evaluated according to the following criteria.

Taber abrasion: An abrasion test was performed using a wear tester specified in JIS K7204 under the conditions of a load of 500 gf and a number of rotations of 1,000. ◎ is good, Δ is slightly bad, and × is bad.

Weather resistance: Using a WS-type sunshine carbon (manufactured by Suga Test Instruments) indicated in JIS A1415-1977, an accelerated exposure test for 5000 hours was performed, and the appearance change was compared with that of the storage test piece. The case where the appearance was almost unchanged from the appearance of the storage test was indicated by ◎, and the case where the appearance was slightly changed was indicated by ○.

Bendability: A steel round bar having a diameter of 2 mm is arranged at the center of a test piece having a length of 100 mm, a width of 50 mm and a thickness of 2 mm, and the round bar is used as a fulcrum.
A bending process was performed at 80 ° C., and the presence or absence of cracks / separation occurring at the bent portion at that time was examined.

From the above two and three, it is clear that the fluororesin laminated film according to the present invention is extremely excellent.

〔The invention's effect〕

In the fluororesin laminated film of the present invention, a film in which a printing layer made of a fluororesin composition is firmly laminated on the surface of the film is formed.

Further, the laminated film of the present invention is excellent in various physical properties such as decorativeness, designability, weather resistance, and stain resistance, and is used as a marking film, a solar film, a release film, a weather-resistant laminate film, and a weather-resistant metal laminate film. It is an excellent film.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a partial cross-sectional view schematically showing a resin-coated metal of a reference example using a laminated film of the present invention. 1 ... metal plate 2 ... fluororesin layer 3 ... printing layer

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Naotake Osaki 469 Motoshin, Uozu-shi, Toyama Examiner Ken-ichi Kamono (56) References Jikai Sho 63-3372 (JP, U) (58) Fields investigated (Int. Cl. ⁶ , DB name) B32B 15/08 B32B 27/30

Claims (5)

(57) [Claims] 1. A fluororesin laminate film comprising a fluororesin composition and a printed layer on at least one surface of the fluororesin film. 2. The fluororesin laminate film according to claim 1, wherein said fluororesin film is an ethylene-tetrafluoroethylene copolymer. 3. The fluororesin laminated film according to claim 1, wherein the surface tension of the surface of the fluororesin film in contact with the printing layer is 35 dynes / cm or more. 4. The fluororesin laminate film according to claim 1, wherein said fluororesin composition has a thixotropic index (TI value) of 1.5 to 8. 5. The fluororesin laminate film according to claim 1, wherein the printing layer is formed using a fluororesin composition having a solids melt flow index of 1 to 500.