JPH0811268A - Fluororesin laminate - Google Patents

Abstract

PURPOSE:To prevent optical degradation of a base material and its discoloration from occurring over a long period of time by a method wherein a layer consisting of hardened material of rigid type fluororesin is laminated on a surface-treated surface for improving adhesion in the fluororesin layer of which a fluorine content is specified, and ultraviolet-absorbent is contained in that layer. CONSTITUTION:In a laminate wherein a layer A consisting of fluororesin of at least 45wt.% fluorine content, and a rigid type fluororesin layer B having a polymerization unit based on fluoroolefins and a polymerization unit based on a monomer having a functional group are provided, the layer A has a treated surface for improving adhesion, the layers A, B are laminated via that surface, and an ultraviolet absorbent is contained in the layer B. The fluororesin is preferably ethylene/tetrafluoroethylene copolymer, tetrafluoroethylene/ hexafluoropropylene copolymer, etc. The rigid type fluororesin is preferably solvent-soluble type fluororesin selected from a group of tetrafluoroethylene and chlorotrifluoroethylene.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to stain resistance, chemical resistance,
The present invention relates to a fluororesin laminate having ultraviolet ray absorbing performance in addition to the characteristics of the fluororesin such as non-adhesiveness and weather resistance.
Furthermore, the present invention relates to the above-mentioned fluororesin laminate having transparency.

[0002]

2. Description of the Related Art Fluororesin films are excellent in stain resistance, chemical resistance, non-adhesiveness and weather resistance. This fluororesin film is used as a protective film for various base materials by taking advantage of its characteristics. Examples of the base material include a steel plate, a polyvinyl chloride resin plate, an ABS resin plate and a polycarbonate resin plate. When the fluororesin film is used as the protective film, various base materials and the fluororesin film are usually laminated so that the fluororesin film is the outermost layer.

When the fluororesin film and various base materials are laminated, a means such as corona discharge treatment of the surface of the fluororesin film or bonding the both with an adhesive is used in order to enhance the adhesive force between the two. Has been adopted. However, when a transparent fluororesin film is adhered to a base material with an adhesive, the adhesive layer and the base material are deteriorated and discolored by the ultraviolet rays that have passed through the fluororesin layer, resulting in peeling of the fluororesin film and designability of the base material. There is a problem that

Further, in the field of agricultural house and horticultural house members, food packaging materials, etc., it has stain resistance, chemical resistance, non-adhesiveness, weather resistance, etc., as well as ultraviolet absorption and visible light. A film material having transparency is desired. A method of adding an organic ultraviolet absorber to a transparent fluororesin film can be considered, but the following drawbacks are recognized in this method. That is, since the molding temperature of the fluororesin is generally high, the organic ultraviolet absorber is easily volatilized during film molding, and the compatibility of the fluororesin and the ultraviolet absorber is poor, so that the ultraviolet absorber is There are problems such as crystallization and becoming opaque, leaching of the ultraviolet absorber during long-term use, and so-called bleed-out phenomenon.

The polyvinyl fluoride resin can be formed into a film at a relatively low forming temperature. Therefore, some organic UV absorbers may be used during film forming of polyvinyl fluoride resin. In addition, polyvinyl fluoride resin,
It has good compatibility with such an organic ultraviolet absorber. Therefore, such an organic ultraviolet absorber has almost no problem of volatilization during film formation of polyvinyl fluoride resin, and the bleed-out phenomenon is relatively unlikely to occur. However, since the polyvinyl fluoride resin has a low fluorine content, it is difficult to exhibit sufficient chemical resistance, non-adhesiveness, and stain resistance, and also the transparency is insufficient.

On the other hand, metal oxides such as titanium oxide and zinc oxide are known as inorganic ultraviolet absorbers. In particular, the ultraviolet absorber composed of fine particles of metal oxide does not impair the transparency of the synthetic resin film and is unlikely to cause a bleed-out phenomenon when it is used by adding it to a synthetic resin because it is fine particles. However, when the metal oxide fine particles are added to the fluororesin to form a film, the particle size increases due to the aggregation of the metal oxide fine particles during melt-kneading with the fluororesin, and the resulting film becomes opaque. Moreover, the metal oxide having an increased particle size impairs the surface characteristics of the fluororesin film.

When the fluororesin film is adhered to the base material with an adhesive, a method of adding an ultraviolet absorber to the base material or the adhesive layer to be protected may be considered. According to this method
Although the problems of volatilization and bleed-out of the ultraviolet absorber can be solved, it does not solve the problem that the base material itself and the adhesive layer itself gradually deteriorate. Furthermore, the adhesiveness between the fluororesin film and the adhesive is not sufficient, and no adhesive has been developed which exhibits sufficient adhesiveness to a fluororesin having a high fluorine content.

Further, a synthetic resin film coated with an ultraviolet absorbing paint is known. For example, JP-A-4-1521
Japanese Patent No. 31 discloses a method of coating a surface of a synthetic resin film made of polyvinylidene chloride resin, polyethylene terephthalate, polycarbonate resin or the like with an ultraviolet absorbing paint in which zinc oxide fine particles are dispersed. However, in this method, since the coating film is formed on the surface of the synthetic resin film, the surface characteristics of the synthetic resin film are impaired. In particular, when this method is applied to a fluororesin film, the surface properties are adversely affected, the adhesion between the fluororesin film and the coating film is insufficient, and the problem of deterioration of the coating film itself remains. .

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a fluororesin laminate having not only the excellent characteristics of fluororesins but also the ability to block ultraviolet rays. Another object of the present invention is to provide the surface of the base material with excellent properties of the fluororesin, to protect the base material from photodegradation and discoloration, and in addition, to provide a highly transparent fluororesin laminate. To provide the body.

[0010]

[Means for Solving the Problems] In order to solve the above problems, the present invention provides a fluorine content of 45% by weight.
A laminate having a layer (A) composed of the above fluororesin and a layer (B) composed of a cured product of a curable fluororesin containing a polymerized unit based on a fluoroolefin and a polymerized unit based on a monomer having a functional group. The layer (A) has a surface-treated surface for improving adhesion, the layer (A) and the layer (B) are laminated on the surface-treated surface, and the layer (B) absorbs ultraviolet rays. The present invention provides a fluororesin laminate characterized by containing an agent.

In the present invention, the layer (A) comprises a fluororesin having a fluorine content of 45% by weight or more. A fluorine resin having a fluorine content of less than 45% by weight has insufficient stain resistance, chemical resistance, non-adhesiveness and weather resistance, and particularly non-adhesiveness,
Insufficient stain resistance. The fluorine content is preferably 50% by weight or more, and particularly preferably 55% by weight or more. Examples of such fluororesin include ethylene / tetrafluoroethylene copolymer (hereinafter referred to as ETFE), tetrafluoroethylene / hexafluoropropylene copolymer (hereinafter referred to as FEP) or tetrafluoroethylene / perfluoro (propyl). A vinyl ether) type copolymer (hereinafter referred to as PFA) is preferable.

ETFE has a molar ratio of tetrafluoroethylene polymer units / ethylene polymer units of 30/70 to.
ET of 70/30, preferably 40/60 to 60/40
FE is illustrated. The ETFE may be obtained by copolymerizing, in addition to the above two components, one or more additional components such as a fluorine-containing olefin and a hydrocarbon olefin. This additional component includes propylene,
Α-olefins such as 1-butene, hexafluoropropylene, vinylidene fluoride, (perfluorobutyl) ethylene, fluorine-containing olefins such as trifluorochloroethylene, perfluoro (ethyl vinyl ether), perfluoro (methyl vinyl ether), Examples thereof include fluorine-containing vinyl ethers such as perfluoro (propyl vinyl ether), and fluorine-containing acrylates. When these additional components are copolymerized, the ETF should be within the range not exceeding 45% by weight.
Copolymerization in E is preferably 50 mol% or less. In some cases, the amount may be such that an additional component is copolymerized in a small amount of 10 mol% or less to modify ETFE.

Although the molecular weight of ETFE is not particularly limited,
A volume flow rate of about 10 to 300 mm ³ / sec is suitable as a standard. The volume flow velocity here is 300 ° C under a load of 30 kg using a Koka type flow tester.
In / cm ^2, diameter 1 mm, to flow out from a nozzle of length 2 mm, capacity of ETFE flowing per unit time (sec) (mm
It is a value represented by ³ ).

The FEP has a molar ratio of tetrafluoroethylene polymer units / hexafluoropropylene polymer units of 70/30 to 99/1, preferably 80/20 to 95.
/ 5 FEP is illustrated. The FEP may be one obtained by copolymerizing, in addition to the above two components, one or more additional components such as a fluorine-containing olefin and a hydrocarbon olefin. As the additional components, propylene, α-olefins such as 1-butene, vinyl fluoride, vinylidene fluoride, (perfluorobutyl) ethylene, fluorine-containing olefins such as trifluorochloroethylene, perfluoro (ethyl vinyl ether). , Fluorine-containing vinyl ethers such as perfluoro (methyl vinyl ether) and perfluoro (propyl vinyl ether). When these additional components are copolymerized, it is sufficient that the FEP is modified.
It is preferable to copolymerize below.

The molecular weight of FEP is not particularly limited, but a volume flow rate of about 0.5 to 300 mm ³ / sec is suitable as a standard. The volumetric flow rate here is 380 ° C. under a load of 7 kg / using a Koka type flow tester.
The capacity (mm ³ ) of FEP that flows out from a nozzle with a diameter of 2 mm and a length of 8 mm in cm ² , and flows out in a unit time (second).
It is a value represented by.

Examples of PFA include PFA having a molar ratio of tetrafluoroethylene polymer units / perfluoro (alkyl vinyl ether) polymer units of 80/20 to 99.5 / 0.5, preferably 90/10 to 99/1. To be done. Examples of perfluoro (alkyl vinyl ether) include perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (n-heptyl vinyl ether) and the like. Considering the physical properties of the copolymer, perfluoro (propyl vinyl ether) is preferable. As PFA, in addition to the above two components, 1
One or two or more kinds of a small amount of fluorine-containing olefins, hydrocarbon-based olefins, and other additional components may be copolymerized. Examples of this additional component include α-olefins such as propylene and 1-butene, fluorine-containing olefins such as vinyl fluoride, vinylidene fluoride, (perfluorobutyl) ethylene, trifluorochloroethylene, and hexafluoropropylene. To be done. When these additional components are copolymerized, it is sufficient to modify the PFA, and it is preferable to copolymerize at 10 mol% or less.

The molecular weight of PFA is not particularly limited, but a volume flow rate of about 0.5 to 300 mm ³ / sec is suitable as a standard. The volumetric flow rate here is 380 ° C. under a load of 7 kg / using a Koka type flow tester.
The capacity (mm ³ ) of PFA flowing out from a nozzle having a diameter of 2 mm and a length of 8 mm in cm ² , and flowing out in a unit time (second).
It is a value represented by.

The fluororesin of the layer (A) is not particularly limited as long as it has a fluorine content of 45% by weight or more, and various fluororesins other than the above ETFE, FEP and PFA are adopted. Can be done. For example, as the fluororesin having high transparency, a polymer having a fluorinated alicyclic structure may be mentioned. This polymer is obtained by polymerizing a monomer having a fluorine-containing ring structure, or is obtained by cyclopolymerizing a fluorine-containing monomer having at least two polymerizable double bonds. A polymer having a ring structure is exemplified.

The polymer having a fluorinated alicyclic structure in its main chain is, for example, perfluoro (2,2-dimethyl-1,3).
-Dioxole) or the like having a fluorine-containing ring structure monomer homopolymerized, or a monomer having this fluorine-containing ring structure and a radical polymerizable monomer such as tetrafluoroethylene are copolymerized (Japanese Patent Publication No. 63- 18964, etc.). Also,
The polymer having a fluorinated alicyclic structure in the main chain is obtained by cyclopolymerizing a fluorinated monomer having at least two polymerizable double bonds such as perfluoro (allyl vinyl ether) and perfluoro (butenyl vinyl ether). Alternatively, it can be obtained by copolymerizing this fluorine-containing monomer with a radical-polymerizable monomer such as tetrafluoroethylene (see JP-A-63-238111 and JP-A-63-238115). Furthermore, the polymer having a fluorinated alicyclic structure in the main chain,
It can also be obtained by copolymerizing a monomer having a fluorinated ring structure and a fluorinated monomer having at least two polymerizable double bonds. As the polymer having a fluorinated alicyclic structure in its main chain, a polymer having a ring structure content of 20% by weight or more is particularly preferable in terms of transparency and mechanical properties.

The thickness of the layer (A) is not particularly limited, but in order to obtain high transparency, it is preferably 5 to 500 μm, and particularly preferably 1 considering the mechanical properties and cost of the laminate.
0 to 200 μm is adopted. Further, when the fluororesin laminate of the present invention is applied as a protective film for various base materials, the base material has mechanical properties such as strength to further reduce the thickness of the layer (A). You can also

The layer (A) has a surface which has been subjected to a surface treatment for improving adhesion. As the surface treatment method, the surface treatment method usually used for improving the adhesiveness of the fluororesin is not particularly limited and can be adopted over a wide range. For example, corona discharge treatment, metallic sodium treatment, mechanical surface roughening treatment, excimer laser treatment and the like can be adopted. Corona discharge treatment is particularly preferable. The surface change when fluorocarbon resin is subjected to corona discharge treatment is quite different from the surface of a plastic containing no fluorine. As a result of tracing the surface by ESCA (electron spectroscopy) analysis, the oxygen content is increasing and the fluorine content is decreasing. Therefore, it is true that the fluorine atom is decreasing and at the same time, the polarity of the oxygen atom as a constituent component It is known that the group has been introduced.

It is advantageous in terms of manufacturing process that the corona discharge treatment is carried out sequentially by disposing a corona discharge treatment machine in the fluororesin film molding line. The processing conditions are selected according to the type of film to be processed and the desired degree of processing. Although not particularly limited, it is preferable to perform the treatment at a strength of 0.1 to 10 kW for about 0.5 to 100 m ² / min.

In the present invention, the layer (B) is composed of a cured product of a curable fluororesin containing a polymerized unit based on a fluoroolefin and a polymerized unit based on a monomer having a functional group. As the curable fluororesin for the layer (B), a solvent-soluble fluororesin is preferably adopted. Since the curable fluororesin of the layer (B) contains the polymerized units based on fluoroolefins, it has excellent weather resistance. Therefore, the problem of deterioration is not recognized in the layer (B) itself. Further, since the curable fluororesin of the layer (B) contains a polymerized unit based on a monomer having a functional group, it can interact with a polar group such as a carboxyl group introduced into the surface-treated surface of the layer (A). Due to the action, high adhesion with the layer (A) is exhibited. Furthermore, since the curable fluororesin of the layer (B) has polymerized units based on fluoroolefins, its polarity is suppressed to be relatively low. Therefore, the layer (B) has a high affinity with the layer (A) having a relatively low polarity, and exhibits higher adhesiveness with the layer (A).

The curable fluororesin in layer (B) contains 20 mol% of polymerized units (1) based on at least one fluoroolefin selected from the group consisting of tetrafluoroethylene and chlorotrifluoroethylene.
The content of the polymer units (2) based on the monomer having a functional group is 1 to 80 mol%, and the total of the polymer units (1) and the polymer units (2) is 30 mol% or more based on all polymer units The solvent-soluble fluororesin containing the above is particularly preferable. If the content of the polymerized units (1) is less than 20 mol%, it is disadvantageous in terms of weather resistance as a curable fluororesin, so that it is preferably about 25 to 70 mol%.

In the preferred curable fluororesin for the layer (B), examples of the monomer giving the polymerized unit (2) include monomers having a polymerizable site such as vinyl group, allyl group, acryloyl group and methacryloyl group. To be Specific examples include olefins, vinyl ethers, vinyl esters, allyl ethers, allyl esters, acrylic acid esters, and methacrylic acid esters,
A monomer having a functional group together with a polymerizable site is exemplified. The content of the polymerized unit (2) is preferably 10 to 65.
Mol%.

The functional group in the polymerized unit (2) can be arbitrarily selected. Specifically, functional groups containing active hydrogen such as hydroxyl group, carboxyl group, amino group, amide group, carboxylic acid halide group, carboxylic acid anhydride group, epoxy group, alkoxysilyl group, isocyanate group, nitrile group, etc. Examples thereof include unsaturated bonds different in polymerizability from the polymerizable site involved in copolymerization. The unsaturated bond as the functional group has a different polymerizability from the polymerizable site of the monomer giving the polymerized unit (2).

The monomer giving the polymerized unit (2) is a monomer having both the above-mentioned polymerizable site and functional group. Specifically, hydroxybutyl vinyl ether, hydroxyethyl allyl ether, hydroxyethyl acrylate, hydroxyethyl (meth) acrylate, ethylene glycol monoallyl ether, acrylic acid, maleic acid, N-dimethylaminoethyl (meth) acrylamide, t-butyl. Examples thereof include aminoethyl (meth) acrylate, maleic anhydride, phthalic anhydride, glycidyl vinyl ether, glycidyl (meth) acrylate, vinyltrimethoxysilane, and trimethoxysilylpropyl vinyl ether.

The functional group in the polymerized unit (2) can be converted into another functional group after copolymerization with the monomer giving the polymerized unit (1). Specifically, a hydroxyalkyl vinyl ether, a hydroxyalkyl allyl ether, a reaction product of acrylic acid and a polyhydric alcohol, a reaction product of glycidyl allyl ether and an alkanolamine or a phenolic compound, a hydroxyl group-containing compound composed of allyl alcohol or the like is an alkylene. Examples thereof include a compound obtained by addition reaction of oxide, and a compound obtained by reacting a compound having a group capable of reacting with the above functional group such as a hydroxyl group, an alkoxysilyl group and a carboxyl group.

The number average molecular weight of the solvent-soluble fluororesin is 5
000 to 20000 is applied. Number average molecular weight is 20
If it exceeds 000, it becomes insoluble in the solvent, and if it is less than 5,000, the characteristics of the coating film and the viscosity of the solution dissolved in the solvent are low, and dispersion of ultrafine particles of metal oxides such as zinc oxide as an ultraviolet absorber and coating of the dispersion liquid are performed. Not preferable.

Here, when the functional group of the solvent-soluble fluororesin of the present invention is a hydrolyzable silyl group or an isocyanate group, it can be cured with moisture and can be used in one liquid. Further, in the case of a functional group containing active hydrogen such as a hydroxyl group, an amino group and a carboxyl group, the reaction with the polyvalent isocyanate generally used as a curing agent is rapid.

As the monomer other than the polymerized units (1) and (2) constituting the solvent-soluble fluororesin, a monomer copolymerizable with tetrafluoroethylene or chlorotrifluoroethylene can be adopted. For example, olefins such as ethylene and propylene, ethyl vinyl ether, cyclohexyl vinyl esters, allyl ethers, allyl esters, acrylic acid esters, methacrylic acid esters, hexafluoropropylene, vinyl fluoride, vinylidene fluoride, trifluoro ethylene,
Examples thereof include fluoroalkyl ethylene and fluoro vinyl ether. The coating thickness of this layer (B) is 1 to 100 μm, preferably 3 to 30 μm, which provides transparency.

The ultraviolet absorber used in the present invention may be any one that is compatible with the solvent-soluble fluororesin, such as benzotriazole compounds, salicylate compounds, benzophenone compounds, cyanoacrylate compounds. Inorganic metal oxide compounds and many other known compounds can be used.

Specifically, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-
Di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2,4-hydroxybenzophenone, 2-hydroxy-4-n-octoxy. Benzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, phenyl salicylate, 4-t-butylphenyl salicylate, ethyl-2-cyano-3,
3'-diphenyl acrylate, methyl-2-cyano-
Examples thereof include organic UV absorbers typified by 3-methyl-3- (p-methoxyphenyl) acrylate, and inorganic UV absorbers typified by metal oxide fine particles such as cerium oxide, titanium oxide, and zinc oxide.

The amount of the above ultraviolet absorber added is 1 to 200 parts by weight, based on 100 parts by weight of the solvent-soluble fluororesin.
Preferably 5 to 150 parts by weight are applied. If the added amount is too large, the transparency is deteriorated due to aggregation and crystallization of the ultraviolet absorber, and if the added amount is too small, the ultraviolet rays are sufficiently shielded, which is not preferable. In particular, metal oxides are excellent in weather resistance of the ultraviolet absorbent itself and bleed-out resistance during use, and it is particularly preferable to use fine particle zinc oxide having excellent transparency.

The solvent-soluble fluororesin is dissolved in aromatic hydrocarbons such as xylene and toluene, esters such as butyl acetate, ketones such as methyl isobutyl ketone, and saturated hydrocarbons such as n-hexane and ligroin. Used. At that time, it is necessary to uniformly disperse the zinc oxide fine particles having a particle diameter of 0.1 μm or less. Therefore, for example, use a ball mill, a triple roll, a high-speed impeller mill, a paint shaker, a homogenizer, an ultrasonic disperser, or the like to disperse them. Is desirable.

When the coating material obtained as described above is applied to the surface of the film substrate, it can be applied by a usual application method such as gravure printing. Further, when such a zinc oxide is added to the solvent-soluble fluororesin, the use of a dispersion stabilizer improves the dispersibility and is useful for improving the transparency and the ultraviolet absorbing performance.

When the fluororesin laminate of the present invention is used as a laminate having a two-layer structure, it is suitable as an ultraviolet-shielding transparent fluororesin film for agricultural greenhouses, food packaging materials and the like.

On the other hand, when a laminate comprising at least two layers is laminated on a steel plate, polyvinyl chloride resin plate, ABS resin plate, polycarbonate resin plate or other building interiors and exteriors, marking films, highway sound insulation walls, etc. It is possible to use an adhesive, an adhesive, a hot melt, but if a solvent-soluble weather-resistant fluororesin having adhesiveness is applied, the layer (B) can also serve as an adhesive layer and an ultraviolet shielding layer. is there.

[0039]

【Example】

[Example 1] Particle diameter of 0.05 μm as an ultraviolet absorber
50 parts by weight of the following zinc oxide fine powder, 50 parts by weight of solvent-soluble fluororesin-1 (polymerization unit composition: chlorotrifluoroethylene / ethyl vinyl ether / hydroxybutyl vinyl ether = 50/43/7 mol%, number average molecular weight 20000) And 145 parts by weight of toluene were uniformly mixed with a homogenizer to obtain a coating material composed of a solvent-soluble fluororesin in which fine particles of zinc oxide were dispersed. This paint is 25μm thick
Corona discharge treated ETFE film (polymerization unit composition tetrafluoroethylene / ethylene / (perfluorobutyl) ethylene = 52.0 / 46.5 / 1.5 mol%,
After coating with a bar coater at a volume flow rate of 60 mm ³ / sec), the coating was heated at 80 ° C. for 20 minutes to form a coating film having a thickness of 4 μm. Next, a white marking film made of polyvinyl chloride was laminated on the film side of the fluororesin paint coating of this film to obtain a laminate.

Example 2 Solvent-soluble fluororesin-1 was replaced with solvent-soluble fluororesin-2 (polymerization unit composition: chlorotrifluoroethylene / vinyl acetate / ethylene glycol monoallyl ether = 45/45/10 mol%). , Number average molecular weight 18,000), but in the same manner as in Example 1 to obtain a laminate.

[Example 3] Solvent-soluble fluororesin-1 was replaced with solvent-soluble fluororesin-3 (polymerization unit composition: tetrafluoroethylene / cyclohexyl vinyl ether / ethyl vinyl ether / hydroxybutyl vinyl ether = 50).
/ 15/25/10 mol%, number average molecular weight 15000)
A laminated body was obtained in the same manner as in Example 1 except that

Example 4 A laminate was obtained in the same manner as in Example 1 except that the ultraviolet absorber was 5 parts by weight of 2-hydroxy-4-n-octoxy-benzophenone and the thickness of the coating film was 20 μm. .

Example 5 An ETFE film having a thickness of 25
A laminated body was obtained in the same manner as in Example 1 except that the FEP film subjected to corona discharge treatment of μm (polymerization unit composition tetrafluoroethylene / hexafluoropropylene = 90/10 mol%, volume flow rate 16 mm ³ / sec) was used.

Example 6 An ETFE film having a thickness of 25
PFA film subjected to corona discharge treatment of μm (polymerization unit composition: tetrafluoroethylene / perfluoropropyl vinyl ether = 98.5 / 1.5 mol%, volume flow rate: 15 m
m ³ / sec), but in the same manner as in Example 1 except that the laminate was obtained.

[Comparative Example 1] A polyvinyl fluoride film (trade name: Tedler TUT10BG3, manufactured by DuPont) containing an ultraviolet absorber was laminated on a white marking film made of polyvinyl chloride to obtain a laminate.

Comparative Example 2 A laminate was obtained in the same manner as in Example 1 except that the ETFE film was replaced with a transparent vinyl chloride resin film having a degreased surface and a thickness of 50 μm.

[Comparative Example 3] A laminate was obtained in the same manner as in Example 1 except that the solvent-soluble fluororesin-1 was replaced with an acrylic urethane resin.

Table 1 shows the evaluation results of the characteristics of the laminates of Examples 1 to 6 and Comparative Examples 1 to 3. The method of each test is shown below.

[Light Transmittance] Using a self-recording spectrophotometer, the transmittance at a wavelength of 400 nm of the fluororesin laminate excluding the polyvinyl chloride marking film as the substrate was measured.

[Staining resistance] The degree of staining (no change at all: ◯, slight change: Δ, strong change: ×) was visually evaluated according to JIS K-6902.

[Weather resistance] 2 using a super UV tester
The laminate after 00 hours was visually observed (no change at all: ○, slight change: Δ, strong change: ×).

[Chemical resistance] 35% HCl, 98% concentrated H ₂
Each of the five chemicals of SO ₄ , 50% NaOH, 28% ammonia water, and aniline was dropped onto the upper layer of the laminate, and the appearance after 24 hours at room temperature (23 ° C.) (no change at all:
○, slight change: △, strong change: ×) were visually judged.

[Adhesion] The adhesion between the coating film and the film was measured according to the method of ASTM-3359: (1) initial stage,
(2) Super UV test The measurement was made after each of the treatments for 200 hours, and the number of remaining squares was evaluated.

[0054]

[Table 1]

[0055]

The fluororesin laminate of the present invention has the original stain resistance, chemical resistance and weather resistance of the fluororesin.
It has an excellent ability to block UV rays. When the transparent fluororesin laminate is used for the protective coating of the substrate, the design of the substrate is utilized, and the photodegradation or discoloration of the substrate is prevented for a long period of time. Furthermore, when the protective coating is applied via an adhesive, the optical deterioration and discoloration of the adhesive can be prevented for a long period of time.

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Claims (8)

[Claims] 1. A cured product of a curable fluororesin containing a layer (A) comprising a fluororesin having a fluorine content of 45% by weight or more and a polymerized unit based on a fluoroolefin and a polymerized unit based on a monomer having a functional group. And a layer (A) having a surface-treated surface for improving adhesion, wherein the layer (A) and the layer (B) are the surface-treated surfaces. A fluororesin laminate, wherein the fluororesin laminate is laminated, and the layer (B) contains an ultraviolet absorber. 2. The fluororesin laminate according to claim 1, wherein the surface treatment of the layer (A) is corona discharge treatment. 3. The fluororesin laminate according to claim 1, wherein the layer (B) is a cured product obtained by curing the surface-treated surface of the layer (A). 4. The fluororesin laminate according to claim 1, wherein the layer (A) is the outermost layer. 5. The curable fluororesin in layer (B) contains 20 mol% or more of polymerized units (1) based on at least one fluoroolefin selected from the group consisting of tetrafluoroethylene and chlorotrifluoroethylene. , A polymerized unit based on a monomer having a functional group (2)
1 to 80 mol%, and the total amount of the polymerized units (1) and the polymerized units (2) is 30 mol% or more with respect to all polymerized units. ~ The fluororesin laminate according to any one of 4 to 4. 6. The fluororesin in layer (A) is an ethylene / tetrafluoroethylene copolymer, a tetrafluoroethylene / hexafluoropropylene copolymer and a tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer. The fluororesin laminate according to claim 1, which is at least one fluororesin selected from the group consisting of: 7. The fluororesin laminate according to claim 1, wherein the ultraviolet absorber in the layer (B) is zinc oxide. 8. A fluororesin laminate in which the fluororesin laminate according to any one of claims 1 to 7 is laminated on a substrate with layer (A) as the outermost layer.