JPH09277454A - Composite film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite film which is excellent in dripproof and its durability and has stainproof, etc., as a composite film by laminating a cellulosic resin film on one side of a fluororesin film through an adhesive layer. SOLUTION: A cellulosic resin film is laminated on one side of a fluororesin film through an adhesive layer. As the fluororesin, tetrafluoroethylene- hexafluoropropylene copolymer is used preferably in terms of mechanical properties, film making, processability, etc., and above all, a composition consisting mainly of ethylene-tetrafluoroethylene copolymer is desirable. The cellulosic resin is cellulose or its ether, ester or other derivatives. Among them, surface- saponified cellulose acetate fibers are preferable especially in view of dripproofing properties.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composite film. More specifically, it relates to a composite film made of a fluororesin film and having excellent dew condensation prevention properties.

[0002]

2. Description of the Related Art In recent years, the spread of agricultural houses has been remarkable, and they are widely used for forcing cultivation and suppression cultivation of vegetables, fruits, flowers and the like.

As a covering material for these agricultural houses, plastic films such as polyethylene film, ethylene-vinyl acetate copolymer film, polyvinyl chloride film and polyester film, which are light and inexpensive and easy to construct, have been used. Due to the pursuit of economic efficiency and labor saving of agricultural houses, there has been a demand for even more durable covering materials.

As such a covering material, a fluororesin film having the best weather resistance among plastic films has been rapidly applied, and although it is disadvantageous in price compared to other kinds of covering materials, it can be used. It is expanding.

The fluororesin film is not only excellent in mechanical strength and light transmittance required as a covering material for agricultural houses, but also existing tunnel houses, pipe houses,
Although it can be easily spread on a large steel house, etc., as a covering material for agricultural houses, the water vapor emitted from soil and plants aggregates on the inner surface of the house to form fine water droplets, and these water droplets have a light transmittance. There is a need for so-called drip-proof treatment that prevents fogging in the house from causing various harmful effects such as deterioration.

This drip-proof treatment is often applied to the film itself before the house is stretched, and is generally carried out by coating a drip-proof agent on the film surface.

Various investigations have been conventionally made on the fluororesin film by such a method, and examples of the composite film having the drip-proof layer as described above include, for example, JP-A-5-310973 and JP-A-5-103973. Japanese Patent Laid-Open No. 5-59202 and the like are disclosed.

[0008]

However, in the conventional composite film, since the drip-proof layer formed on the film surface is washed away with the passage of time, the drip-proof effect is not long-lasting. .

For this reason, the drip-proofing agent had to be applied again by spraying or the like, which required a considerable amount of labor.

Furthermore, the time until the drip-proof effect is exhibited,
That is, it was not sufficient in terms of fast-acting effect.

Thus, it has been technically difficult to satisfy both the rapid effect and the durability required for the drip-proof property.

The present invention solves the above problems,
Aims to provide a composite film having excellent drip-proof property and durability as well as antifouling property as a composite film

[0013]

The composite film of the present invention for this purpose comprises a fluororesin film and a fibrous resin film laminated on one surface of the fluororesin film via an adhesive layer.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the invention, the material of the fluororesin film is not particularly limited, and various kinds can be used.

As typical examples, a tetrafluoroethylene polymer, an ethylene-4fluoroethylene copolymer, a tetrafluoroethylene-6fluoropropylene copolymer, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer. Two
Vinylidene fluoride polymer, trifluoroethylene polymer, 1
A fluorinated ethylene polymer, a chlorinated monofluorinated ethylene polymer or the like, or a copolymer or a mixture thereof can be used.

However, from the viewpoints of mechanical properties, film-forming property, processability, etc., it is preferable to use tetrafluoroethylene-6-fluoropropylene copolymer and ethylene-4fluoroethylene copolymer, among which ethylene-4 Those containing a fluorinated ethylene copolymer as a main component are particularly preferable.

Incidentally, the main component is 5 out of the resin component itself.
It is 0% or more, more preferably 70% or more, and may appropriately contain other substances.

The resin to be added is not particularly limited, but, for example, a polyolefin resin, an acrylic resin or the like can be used.

If necessary, the fluororesin film may contain suitable additives in an amount that does not impair the effects of the present invention, such as a heat stabilizer, an oxidation stabilizer, a weather stabilizer, an ultraviolet absorber, a pigment, Dyes, inorganic or organic fine particles, dispersants, coupling agents, fillers and the like may be added.

Further, the fluororesin film may be used in any of non-oriented, uniaxially oriented and biaxially oriented, but the oriented film is desirable when mechanical strength is required.

The thickness of the fluororesin film layer is not particularly limited and can be set to an appropriate thickness in the range of about 25 to 500 μm according to the desired characteristics.

The surface roughness and optical characteristics of the fluororesin film are not particularly limited, and may be appropriately set to desired values in consideration of required characteristics.

However, when it is applied to an agricultural house or the like, it is preferable from the viewpoint of transparency that the total light transmittance is preferably 70% or more.

Further, in the present invention, the surface of the fluororesin film is subjected to a surface treatment or an undercoating treatment to improve the adhesion to the antifouling layer, the ultraviolet absorbing layer, the adhesive layer, the water resistance, the solvent resistance and the like. Therefore, it can be used more preferably.

Examples of the surface treatment include corona discharge treatment (in air, nitrogen, carbon dioxide gas, etc.), plasma treatment (high pressure and low pressure), alkali metal solution treatment, high frequency sputter etching treatment and the like.

In the case of surface treatment, the treatment strength is not particularly limited and may be a desired value. As a measure of treatment strength, the surface leakage index of the film measured according to JIS-K-6768. Is preferably 35 dyn / cm or more, and more preferably 40 dyn / cm or more.

In the present invention, the fibrin resin film is a film made of cellulose alone or a cellulose derivative obtained by etherification or esterification of hydroxyl groups existing in cellulose, and various kinds of films can be applied.

Specific examples thereof include nitrocellulose, acetylcellulose, cellulose acetate butyrate, cellulose acetate propionate, and ethylcellulose films made of cellophane and cellulose derivatives, but from the viewpoint of characteristics, acetylcellulose and cellulose acetate. It is preferable to use butyrate,
Among them, those obtained by saponifying the surface of acetyl cellulose are particularly preferable in terms of drip-proof performance.

In the cellulose derivative, the degree of substitution of hydroxyl groups and the degree of polymerization are not particularly limited, but the higher the degree of polymerization, the more preferable in terms of the mechanical properties of the film itself.

If necessary, the fibrous resin film may contain additives such as heat-resistant stabilizers, inorganic or organic colorants, fillers, lubricants, etc. in amounts that do not impair the effects of the present invention. May be.

The thickness of the fibrin-based resin film is not particularly limited, and one having an appropriate thickness is used in the range of about 5 to 200 μm.

The mechanical properties of the film may be desired values, but the optical properties are more preferably 70% or more of total light transmittance.

Further, in the present invention, in order to improve the adhesion, water resistance and the like between the fibrous resin film and the adhesive layer, it is desirable to subject the film surface to a surface treatment or an undercoating treatment.

Examples of the surface treatment include corona discharge treatment and plasma treatment under various atmospheres.

As the undercoating treatment, for example, various kinds of polyester, polyvinyl chloride, poly (meth) acrylic acid ester, polyvinylidene chloride, polyurethane, halogenated polyolefin, epoxy resin and the like, and copolymers and mixtures thereof are used. The thing which apply | coated the easy adhesive agent is mentioned.

In the present invention, when the composite film of the present invention is used outdoors, it is desirable to provide an antifouling layer in order to eliminate the inconvenience caused by surface contamination of the fluororesin film.

The antifouling layer as referred to in the present invention means a layer having a property that it does not stain or is unlikely to stain, a property that stains can be easily removed even if it becomes dirty, and an antifouling layer having the function is a surface. Compounds or resins such as fluorine-based compounds, silicone-based compounds, wax-based compounds, etc., which give water-repellent and oil-repellent action, further surfactants, water-based resins, etc., which give hydrophilicity to the surface to enhance antistatic action and cleaning action, and combinations thereof. An example is a layer made of a mixture or the like.

However, in the present invention, it is most preferable to apply a layer composed of a composition containing an inorganic hydrophilic colloid substance as a main component, particularly in view of antifouling property and durability thereof.

The layer containing the main component means that the content of the layer is 30% or more in the antifouling layer, and may appropriately contain other substances.

The substance to be contained is not particularly limited, but in the present invention, particularly when a surfactant, a lithium silicate and / or a silane derivative, a polymer resin binder, etc. are contained in the antifouling layer, It is more preferable because its antifouling property is improved.

In the present invention, such an antifouling layer is provided on the surface of the fluororesin film.

The inorganic hydrophilic colloidal substance in the present invention includes a metal colloid or an oxide colloid, depending on the element.
Obtained as a hydroxide colloid, a carbonate colloid, a sulfate colloid and the like.

Colloidal silica is typical,
Colloidal alumina, colloidal Fe (OH) ₂ ,
Colloidal Sn (OH) ₄ , colloidal Tio
₂ , colloidal BaSO ₄ and colloidal lithium silicate.

Two or more kinds of these colloidal substances may be used in combination. Incidentally, colloidal silica or colloidal alumina is particularly preferable as the inorganic hydrophilic colloid substance. The above colloidal substance is preferably an aqueous sol type.

Further, as the substances to be added to the inorganic hydrophilic colloidal substance, the preferred surfactants in the present invention include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. Either is fine.

However, it is preferable that the surfactant is appropriately selected in consideration of compatibility with the above-mentioned inorganic hydrophilic colloid, stability, and the like.

For example, when colloidal silica is used, an anionic surfactant and / or nonionic surfactant is preferably used, and when colloidal alumina is used, a cationic surfactant and / or nonionic surfactant is used. Is preferably used.

Furthermore, in the preferred substance lithium silicate and / or silane derivative, the lithium silicate is obtained by melting silicon dioxide and a lithium salt such as lithium carbonate. Represented by

Li ₂ O.SiO ₂ Lithium silicates having different water solubility are obtained depending on the blending ratio of silicon dioxide and lithium salt.

For example, in the general formula, when n is 6 to 10 is insoluble in water, the lithium silicate in this case can be in a colloidal form and can be used as the above-mentioned inorganic hydrophilic colloidal substance. Since lithium silicate in which n is 2 to 5 is water-soluble, it can be used as a binder together with the above-mentioned inorganic hydrophilic colloid substance.

On the other hand, the silane derivative is represented by the following chemical formula 1.

[0052]

Embedded image In the formula, R ₁ is at least one reactive group selected from an amino group, an epoxy group, an epoxy group-containing group, a ureido group, an ammonium group and an ethylenically unsaturated bond-containing group.
It is an alkyl group or an aryl group having one unit. Also R ₂
And R ₃ each represent an alkyl group having 1 to 3 carbon atoms, and R ₂ and R ₃ may be the same or different. Furthermore, n has shown the integer of 1-3.

The silane derivative may be appropriately selected according to the kind of the film support. When it is applied to a substrate such as ethylene-4fluoroethylene copolymer, it is represented by the following chemical formulas 2-4. Epoxy silane derivative having a structure
Alternatively, it is particularly preferable to use a chlorine-based silane derivative having a structure represented by Chemical Formula 5 as a main component from the viewpoint of coatability or the adhesiveness to a resin substrate. (However, m = 1
-10 integer group, n = 0 or 1, R ₂ = carbon number 1 to 1
A hydrocarbon residue selected from an alkyl group of 0, R ₃ = a hydrocarbon residue selected from an alkyl group having 1 to 10 carbon atoms, a phenyl group and a cyclohexyl group).

The use of lithium silicate or a silane derivative is particularly preferable because the antifouling layer is less likely to fall off or peel off and the antifouling effect can be maintained for a long period of time.

[0055]

Embedded image

Embedded image

Embedded image

Embedded image Further, as the polymer resin binder, polyester,
Examples include various substances such as polyvinyl chloride, poly (meth) acrylic acid ester, polyamide, polyurethane, and their copolymers and mixtures. Among them, those using poly (meth) acrylic acid ester are antifouling. It is more preferable in terms of layer adhesion and durability.

The amount of each component in the antifouling layer described above is not particularly limited, but from the viewpoint of antifouling property and durability, 0.5 to 15% by weight of a surfactant, lithium silicate and / or lithium silicate and / or It is preferable that the silane derivative is in the range of 5 to 20% by weight and the inorganic hydrophilic colloid substance is in the range of 65 to 94.5% by weight, and water and / or alcohol and the like are preferably used as the medium of these compositions.

Further, when a polymer resin binder is used in combination, the addition amount is 0.
The amount is preferably 05 to 40 parts by weight, more preferably 0.5 to 20 parts by weight.

Among them, a particularly preferable composition as an antifouling agent is colloidal silica, an ether type nonionic surfactant, R ₁ is an epoxy group or an alkyl group having at least one epoxy group-containing group, and R ₂ is The dispersion medium is an alcohol having 1 to 4 carbon atoms, which contains the aforementioned silane derivative in which R ₃ is an alkyl group having 1 to ₃ carbon atoms.

In the antifouling layer, if necessary, an additive such as an antifoaming agent, an ultraviolet absorber, a coatability improving agent, a pigment, a dye, an antioxidant, or a crosslinking agent is added in an amount that does not impair the effects of the present invention. You may include an agent etc.

The layer thickness of the antifouling layer is not particularly limited, but is preferably 0.01 to 15 μm, more preferably 0.05 to 5 μm for uniform layer formation and handling. It is preferable from the viewpoints of properties and antifouling properties.

The adhesive layer as referred to in the present invention is not particularly limited, and a general adhesive layer, a heat-adhesive resin layer, a pressure-sensitive adhesive layer can be applied, and an adhesive layer having excellent adhesion to each base layer. Can be preferably used.

The general adhesive layer referred to in the present invention is, for example, a thermosetting adhesive such as an epoxy resin type, a urea resin type, a phenol resin type, a polyisocyanate type, a silicone resin type, and various acrylic and methacrylic acid. Examples thereof include thermoplastic adhesives such as ester-based, cyanoacrylic ester-based, and polyamide-based adhesives, and composite polymer-based adhesives such as epoxy resin / nylon resin-based and rubber / phenolic resin-based adhesives.

The thermoadhesive resin layer as referred to in the present invention is a thermoplastic resin, or a mixture thereof, or a resin to which low molecular weight paraffin or the like is added, which is an adhesive resin that melts when heated and solidifies when cooled. Specifically, for example, ethylene and an ethylene-vinyl acetate copolymer resin as a copolymer thereof, an ethylene-acrylate copolymer resin or an ionomer resin, a polyamide resin, a polyester resin, a polypropylene resin, or a polyurethane resin. Resin, polyester urethane resin, vinyl chloride resin,
Examples thereof include polymethacrylic resin.

The adhesive layer in the present invention is not particularly limited, but (1) polymers such as natural rubber, styrene-butadiene rubber, polyisobutylene, polychloroprene, polyacrylate rubber, polyvinyl ether rubber,
(2) A mixture of a polymeric material such as polyvinyl chloride, a copolymer of vinyl chloride and vinyl acetate, polyvinyl butyral, chlorinated rubber, hydrochloric acid rubber, polyacrylic acid ester and its copolymer and a plasticizer, (3) ) Tackifiers such as rosin, rosin ester, coumarone resin, terpene resin, hydrocarbon resin and oil-soluble phenol resin, (4) various additives such as fillers, pigments, antioxidants, stabilizers, etc. ) To (4), various combinations and silicone-based pressure-sensitive adhesives can be mentioned as typical examples.

In the present invention, the thickness of the adhesive layer is not particularly limited and can be a desired value, but it is 1 to 500 μm.
m is preferably in the range of 10 to 100 μm in terms of uniform layer formation, processability such as lamination, and adhesion.

If necessary, the adhesive layer may contain additives such as a plasticizer, a stabilizer, an inorganic or organic lubricant, an ultraviolet absorber and a flame retardant in an amount that does not impair the effects of the present invention. May be.

In the present invention, it is particularly preferable to use a heat-adhesive resin layer as the adhesive layer from the viewpoint of the production of the composite film of the present invention. It refers to one that is 50% or more in the layer.

Among the heat-adhesive resins, polyester resins, polyester urethane resins, vinyl chloride resins and polymethacryl resins are preferably used in the present invention, and polymethacryl resins are particularly preferable.

In the present invention, when the composite film of the present invention is used outdoors, it is desirable to provide an ultraviolet absorbing layer in order to prevent deterioration of the fibrous resin film by ultraviolet rays.

The UV absorbing layer is not particularly limited as long as it has a UV absorbing ability.

In the present invention, such an ultraviolet absorbing layer is preferably provided between the fluororesin film and the adhesive layer.

In the present invention, as the ultraviolet absorbing layer,
A composition mainly containing a mixture of a general polymer binder and an ultraviolet absorber can be preferably used. The main component refers to one that is 50% by weight or more in the layer.

The polymer binder referred to in the present invention is a resin which is selected from a thermoplastic resin or a curable resin and is soluble in an organic solvent or the like, and a resin having a small amount of hydrophilic groups or hydrophilic components is ultraviolet light. It is preferable in terms of water resistance and moisture resistance of the absorbent layer.

Specific examples of the thermoplastic resin include polyester, polyamide, polyesteramide,
Polyvinyl acetal, polyvinyl chloride, poly (meth)
Examples thereof include acrylic acid esters, polyimides, polyurethanes, polycarbonates, polystyrenes, polymethylpentenes, polyolefins, halogenated polyolefins, alkyd resins, polyamideimides, silicon resins, fluororesins, and copolymers thereof.

As the curable resin which is cured by light, heat, oxygen, etc., for example, phenol resin, melamine resin,
Epoxy resins, cross-linked organosilicon resins, etc. may be mentioned.

In the present invention, it is preferable to use a thermosetting resin from the viewpoint of water resistance, solvent resistance, heat resistance, abrasion resistance, mechanical strength, etc. of the ultraviolet absorbing layer, and further, crosslinking can be achieved by using a crosslinking agent together. Is more preferable.

Further, in the present invention, it is preferable to use urethane resin and acrylic copolymer resin among the above-mentioned polymer binders, most preferable is acrylic copolymer resin, and among them, poly (meth) acrylic acid ester copolymer is preferable. It is a polymer. What is a poly (meth) acrylic acid ester copolymer?
A poly (meth) acrylic acid ester copolymer containing a reactive monomer, and such a reactive monomer includes:
As the functional group, for example, a carboxyl group ((meth) acrylic acid or the like), a hydroxyl group (2-hydroxyethyl (meth) acrylate or the like), an amide group ((meth) acrylic acid amide or the like), a glycidyl group ((meth) acrylic) Glycidyl acid, etc.), compounds containing an amino group (2-diethylaminoethyl (meth) acrylate, etc.), and the like.

Examples of the organic solvent for the polymer binder include alcohol-based, carboxylic acid ester-based, ketone-based, aliphatic hydrocarbon, alicyclic or aromatic hydrocarbon-based solvents, and mixed systems thereof. Therefore, it is preferable to select a material that does not adversely affect the coating property and the like.

The ultraviolet absorber used in the present invention has excellent heat resistance, has good compatibility with the above-mentioned polymer binder, can be uniformly dispersed, has little coloring, and has no adverse effect on the resin. Is desirable.

Examples of the ultraviolet absorber include benzophenone type, benzotriazole type, hindered amine type,
Various applications such as oxalic acid system are possible,
Specifically, bis (5-benzoyl-4-hydroxy-
2-methoxyphenyl) methane, 2,2'-4,4'-
Tetrahydroxy-benzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-benzophenone,
2,4-di-t-butylphenyl-3 ′, 5′-di-t
-Butyl-4'-hydroxybenzoate, 2-
(3 ', 5'-ditersialyamyl-2',-hydroxyphenyl) benzotriazole, 2 (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-
Chlorobenzotriazole, 2 (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) benzotriazole, 2-ethoxy-2'-ethyloxacacid bisanilide, 2,4-di-t-butylphenyl-
3 ', 5'-di-t-butyl-4'-hydroxybenzoate, bis (2,2,6,6-tetramethyl-4-
Piperidyl) sebacate, dimethyl succinate 1- (2
-Hydroxyethyl) -4-hydroxy-2,2,6,
Examples thereof include 6-tetramethylpiperidine polycondensation product.

The ultraviolet absorber is not particularly limited, and may be a single type or a combination of two or more types depending on the case.

The content of the ultraviolet absorber in the layer is 0.
The content is preferably from 01 to 50% by weight, more preferably from 0.1 to 20% by weight.

When the content is lower than the above range, it is difficult to obtain a sufficient ultraviolet blocking property, and when the content exceeds the above range, the uniform dispersibility is likely to be lowered.

In the present invention, the laminated thickness of the ultraviolet absorbing layer is
Although not particularly limited, it is preferably from 0.05 to 50 μm, and more preferably from 0.1 to 20 μm in terms of uniformity of the ultraviolet absorbing layer, adhesion, and the like.

If necessary, the ultraviolet absorbing layer may contain additives such as an antifoaming agent, a coatability improving agent, a thickener, an antistatic agent and a dye in an amount that does not impair the effects of the present invention. May be.

In the present invention, it is particularly preferable to use an ultraviolet absorbing acrylic resin as the ultraviolet absorbing layer from the viewpoint of durability and the like, and the composition containing the ultraviolet absorbing acrylic resin as a main component is the ultraviolet ray itself. 50% by weight in the absorption layer
This refers to the above, and other substances may be added as appropriate.

The resin to be added is not particularly limited, but for example, polyester resin, acrylic resin, etc. can be used.

The ultraviolet absorbing acrylic resin used in the present invention is a resin whose composition, production method and the like have already been disclosed, and the details thereof are described in JP-B-43-27737 and JP-A-63-139958. It is described in JP-A-2-180909 and JP-A-3-281685.

Specific examples thereof include a copolymer resin of a reactive benzophenone compound having an ultraviolet absorbing ability and an acrylic monomer having a polymerizable unsaturated group.

Here, the reactive benzophenone-based compound is a benzophenone-based monomer having a copolymerizable unsaturated group in the molecule, for example, 2-hydroxy-4-.
Methacryloxybenzophenone, 2-hydroxy-4
Examples include-(2-hydroxy-3-methacryloxy) propoxybenzophenone, 2-hydroxy-4- (2-methacryloxy) ethoxybenzophenone, 2-hydroxy-4-vinyloxycarbonylmethoxybenzophenone.

Of these, 2-hydroxy-4-methacryloxybenzophenone and 2-hydroxy-4- (2-methacryloxy) ethoxybenzophenone are preferably used from the viewpoint of polymerizability and properties.

The acrylic monomer having a polymerizable unsaturated group is an alkyl acrylate represented by the following chemical formula 6 (R: hydrogen or methyl group, R'is an alkyl group having 1 to 18 carbon atoms), and Alkyl methacrylate, acrylic acid, methacrylic acid, β-hydroxy acrylate,
β-hydroxymethacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, polyoxyethylene glycol monomethacrylate, polyethylene polytetramethylene ether glycol monomethacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylamide, methacrylamide, N-methyl Methacrylamide, Nn-butoxymethyl acrylamide, acid phosphooxyethyl methacrylate, 3-chloro-2
-Acid phosphooxypropyl methacrylate, 3-
Chloro-2-hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, methoxypolyethylene glycol monomethacrylate, 3-acrylamido-2-methylpropanesulfonic acid, N-methylolacrylamide,
N-methylol methacrylamide, polyoxyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dibromoneopentyl glycol methacrylate, At least one selected from tetramethylolmethane triacrylate and the like can be mentioned.

[0093]

[Chemical 6] Above all, the copolymer is preferably an alkyl methacrylate or an alkyl acrylate in terms of its polymerizability, coating film properties, and the like, and examples thereof include methyl methacrylate and ethyl acrylate. Further, it is preferable to use a carboxyl group- or methylol group-containing acrylic monomer in terms of adhesion to the substrate.

In terms of the composition of the ultraviolet absorbing acrylic resin, 2-hydroxy-4-methacryloxybenzophenone or 2-hydroxy-4- (2-methacryloxy) ethoxybenzophenone and an acrylic resin are used as the reactive benzophenone compound. It is preferable in terms of characteristics that the monomer is mainly composed of a combination with methyl methacrylate. Further, when the acrylic monomer is contained in an amount of 20% by weight or more and 80% by weight or less, transparency and coating film characteristics are excellent, and therefore it is more preferable.

As the ultraviolet absorbing acrylic resin, particularly preferable one is UL manufactured by Yushisha Kogyo Co., Ltd.
S-935LH, ULS-680 etc. are illustrated.

The ultraviolet absorbing acrylic resin can be used as an aqueous dispersion or an organic solvent, but in the case of an organic solvent, an organic solvent such as an alcohol, a carboxylic acid ester, a ketone or an aliphatic carbon is used. Examples thereof include hydrogen, alicyclic or aromatic hydrocarbon systems and mixed systems thereof, and it is preferable to select those which do not adversely affect the coating property.

In the present invention, in order to further improve the adhesion, solvent resistance, water resistance, scratch resistance, heat resistance and the like of the adhesive layer and the ultraviolet absorbing layer, it is preferable to add a crosslinking binder to the layer. .

The cross-linking agent as used in the present invention means a functional group existing in the resin or the like constituting the layer, for example, a hydroxyl group,
A carboxyl group, a glycidyl group, a cross-linking reaction with an amide group, etc., and finally a cross-linking agent for forming a layer having a three-dimensional network structure. As a typical example, a methylolated or alkylolated urea-based, melamine-based, Acrylamide,
A polyamide resin, an epoxy compound, an isocyanate compound, a coupling agent, an aziridine compound, etc. can be used.

In the present invention, among these, it is preferable to use an isocyanate compound from the viewpoint of adhesion to the support, crosslinkability and the like.

These cross-linking agents may be used alone or in combination of two or more depending on the case. The amount of the cross-linking agent to be added is appropriately selected depending on the kind of the cross-linking agent, but is usually preferably 0.01 to 50 parts by weight, more preferably 0.2 to 30 parts by weight, based on 100 parts by weight of the resin solid content. . Further, it is more preferable to use a crosslinking catalyst together with the crosslinking binder because crosslinking will proceed further. As the crosslinking catalyst, salts, inorganic substances, organic substances, acid substances, alkaline substances and the like can be used. The amount of the cross-linking agent added is preferably 0.001 to 10 parts by weight, based on 100 parts by weight of the resin solid, and 0.1 to 5 parts by weight.
Parts by weight are more preferred. The coating material containing the additive is cross-linked by heating, ultraviolet rays, electron beams or the like after coating it on the support, but a method by heating is generally used.

In the present invention, for example, in the production of the composite film of the present invention, when workability is deteriorated due to insufficient stickiness or slipperiness during lamination of a fluororesin film and a fibrous resin film, an adhesive layer or It is desirable that the ultraviolet absorbing layer contains inorganic or organic fine particles.

Examples of the inorganic particles include zinc carbonate, zinc oxide, zinc sulfide, talc, carion, heavy / light or synthetic calcium carbonate, titanium oxide, silica, colloidal silica, lithium fluoride, calcium fluoride, barium sulfate. , Alumina, alumina sol, zirconia, calcium phosphate, natural or synthetic swelling or non-swelling mica, etc. can be used, and as the organic particles, for example, polystyrene, polymethylstyrene, polymethoxystyrene, polyvinyl chloride, polyethylene, Polypropylene, polyvinylidene chloride, polymethacrylate, polymethylmethacrylate, polychloroacrylate, styrene-divinylbenzene copolymer, melamine resin, epoxy resin, phenol resin, fluororesin and the like can be used. Although it is possible to use at least one or more selected et al., It is not particularly limited. Further, the fine particles may be in a hollow porous state or a non-hollow porous state. Further, the fine particles may be subjected to a treatment such as adding a functional group such as a glycidyl group or a methylol group to the surface thereof in order to improve the dispersibility in the resin.

The average particle size of the fine particles is 0.01 to 500 μm.
Those in the range are more preferable in terms of handleability, coatability and the like. The content of the fine particles in the layer is preferably 0.1 to 50% by weight, more preferably 1 to 25% by weight. If the content is outside this range, workability is likely to be deteriorated and the adhesion of the laminated product is likely to be deteriorated.

Next, some examples of the method for producing the composite film of the present invention will be described, but the invention is not limited to such examples.

(1) A substrate having an antifouling layer, an ultraviolet absorbing layer and an adhesive layer, which is prepared by coating each film with a predetermined amount of coating liquid in the film forming process of a fluororesin film and then drying. Make a film. In this method, the base film and the fibrin-based resin film are pressure-bonded or pressure-heat-bonded with a laminating roll and heat-treated as necessary.

(2) After winding the fluororesin film as a single film, a coating-drying step is provided to prepare a base film having an antifouling layer, an ultraviolet absorbing layer and an adhesive layer. Hereinafter, a method similar to the above (1) is used.

(3) Coating on a fibrous resin film-
This is a method in which after a drying step is provided to form an adhesive layer, the fluororesin film on which the antifouling layer and the ultraviolet absorbing layer are formed is pressure-bonded or pressure-heat bonded with a laminating roll to be integrated.

The coating method is not particularly limited, and an extrusion laminating method, a melt coating method or the like may be used.
A method such as a gravure coating method, a reverse coating method, a spray coating method, a kiss coating method, a die coating method or a metalling bar coating method can be used because a thin film can be coated at a high speed.

Incidentally, it is desirable that the conditions for drying the coating film and the conditions for heat and pressure bonding be such that they do not adversely affect the various characteristics of each substrate.

Next, when a heat-adhesive resin layer is applied as the adhesive layer, the resin pellets are fed to an extruder and melted at a temperature above the melting temperature and below the temperature at which the resin decomposes, and the above-mentioned film is formed by an extrusion laminating method. A method of forming on the surface or a method of uniformly dissolving the resin in an organic solvent to prepare a solution adjusted to a predetermined amount and coating the solution on the film surface can be preferably used.

[0111]

[Method of measuring and evaluating characteristics] The characteristic value of the present invention is as follows.
According to the following measurement methods and evaluation criteria.

(1) Drip-proof property As for the fast-acting property, the film was placed in a sealed state at an angle of 30 degrees from the horizontal plane on a thermostat kept at a water temperature of 40 ° C., and the initial drip-proof property was observed after 5 minutes. On the other hand, the sustainability is about 2 outdoors.
The roof of a steel house of 2 tsubo was covered with a film at an angle of 15 degrees from the horizontal plane, and the drip-proof performance for 6 months in winter (October to March) was observed under crop cultivation.

In all cases, the criteria were as follows.

◯: Good Δ: Slightly inferior ×: Poor

(2) Antifouling property The degree of dust adhering to the film surface of the steel frame house of the above (1) was comparatively observed over time, and evaluated according to the following criteria.

The evaluation period was similarly set to 6 months.

◯: Good Δ: Slightly inferior (slightly noticeable stains) ×: Poor (stainable stains are noticeable)

[0118]

The present invention will be described with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

Example 1 100 μm thick fluororesin film “TOYOFLON” E
Corona discharge treatment of one surface of TFE (manufactured by Toray Industries, Inc.)
A 80 μm thick triacetate film “Fujitac” (manufactured by Fuji Photo Film Co., Ltd.) whose adhesive surface is treated by corona discharge as a fibrin-based resin film on the treated surface is an epoxy adhesive “Adallite” (manufactured by Ciba-Gaiki) It was laminated via. Next, the laminated body is subjected to a temperature of 60 ° C. and a concentration of 4
The surface of the triacetate film was saponified by immersing it in an aqueous solution of sodium hydroxide of wt% to prepare a composite film. The properties of the obtained composite film were, as shown in Table 1, excellent in drip-proof property.

Example 2 A composite film was prepared in the same manner as in Example 1 except that a commercially available diacetate film having a thickness of 15 μm, the adhesive surface of which was treated by corona discharge, was used as the fibrous resin film based on Example 1. Got As shown in Table 1, the composite film was excellent in drip-proof property.

Example 3 Toluene / methyl ethyl ketone was used as a coating material on the surface of the fluororesin film treated with corona discharge of Example 1 as a diluent solvent, and a saturated thermoplastic polyester resin "Byron" 200 (manufactured by Toyobo Co., Ltd.) was used. And 5 parts by weight of isocyanate compound "Coronate" HX per solid content of the resin
A coating material having a concentration of 20% by weight (manufactured by Nippon Polyurethane Industry Co., Ltd.) was uniformly dissolved to form an adhesive layer having a thickness of 10 μm. Next, a vinylidene chloride resin “Diophan” YJ207DC (manufactured by Mitsubishi Petrochemical Birdish Co., Ltd.) was applied to the corona discharge treated surface of the diacetate film used in Example 2 to a thickness of 2 μm as an undercoat treatment. The treated surface of the film was pressure-bonded with a laminating roll at 150 ° C. through the adhesive layer, heat-treated at 45 ° C. for 24 hours, and then saponified as in Example 1 to obtain a composite film. . As shown in Table 1, the composite film was excellent in drip-proof property.

Example 4 The surface of the fluororesin film of the composite film obtained in Example 3 was subjected to corona discharge treatment, and methanol was used as a stain-proofing agent on the surface of the film, and a colloidal silica (Catalyst Chemical Industry Co., Ltd. )) Isopropyl alcohol dispersion "OSC
AL ″ (a), β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (b), and polyoxyethylene (10 mol) -ularyl ether (c) each had a solid content weight ratio of a: b: Applying a uniform coating material having an active ingredient concentration of 20% by weight mixed so that c = 85: 4: 11,
The coating layer was dried at 100 ° C. to form a 0.4 μm thick antifouling layer. The composite film thus obtained was excellent in drip-proof property and antifouling property as shown in Table 1.

Example 5 Based on Example 3, first, toluene / methyl ethyl ketone was used as a diluting solvent as a coating material on the film surface subjected to corona discharge treatment, and a heat-crosslinking acrylic resin "Cotax" LH681 (Toray Industries, Inc.) was used. And a UV absorber "ADEKA STAB" LA-31 (manufactured by Asahi Denka Kogyo Co., Ltd.) at a solid content weight ratio of 90:10, and a uniform coating material having a concentration of 10% by weight is applied. After being dried for 2 minutes to form an ultraviolet absorbing layer having a thickness of 7.0 μm, a composite film was formed in the same manner as in Example 3 except that an adhesive layer was provided on the ultraviolet absorbing layer by the same method as in Example 3. Got As shown in Table 1, the composite film was excellent in drip-proof property.

Example 6 Based on Example 3, toluene / methyl ethyl ketone was used as a coating material as a diluent solvent on the surface of a fluororesin film which had been subjected to corona discharge treatment, and an ultraviolet-absorbing acrylic resin (produced by Yatasha Yushi Kogyo Co., Ltd.). Manufactured by ULS-935LH) and 5 parts by weight of the isocyanate compound "Coronate" HX per solid content of the resin are applied to apply a uniform coating material having a concentration of 15% by weight, and then the coating layer is dried at 120 ° C. for 1 minute to give a thickness of 2.
A composite film was obtained in the same manner as in Example 1 except that an ultraviolet absorbing layer having a thickness of 8 μm was provided and then an adhesive layer was provided on the ultraviolet absorbing layer by the same method as in Example 3. As shown in Table 1, the composite film was excellent in drip-proof property.

Example 7 Based on Example 3, polyester urethane resin “Vylon” UR1400 (manufactured by Toyobo Co., Ltd.) was used as an adhesive layer, and the isocyanate compound “Coronate” HX was added to the resin in an amount of 5 per resin.
A composite film was obtained in the same manner as in Example 3, except that a coating material having a concentration of 20% by weight added in parts by weight was applied. As shown in Table 1, the composite film was excellent in drip-proof property.

Comparative Example 1 On the corona discharge treatment of the fluororesin film used in Example 1, polyvinyl alcohol “Dencapovar” K-24E (manufactured by Denki Kagaku Kogyo Co., Ltd.) was dissolved in water as a drip-proofing agent. Apply a coating material with a concentration of 5% by weight, and apply the coating layer at 110 ° C.
And dried to form a 0.7 μm-thick drip-proof layer. As shown in Table 1, the composite film thus obtained is inferior in drip-proof property.

Comparative Example 2 On the corona discharge treatment of the fluororesin film used in Example 1, colloidal silica "Cataroid" was used as a drip-proof agent.
S-30L (manufactured by Catalysts & Chemicals Co., Ltd.) and nonionic surfactant "NONION" NS-210 (NOF CORPORATION)
A composite film having a drip-proof layer having a thickness of 0.2 μm, which is obtained by applying a coating material having a concentration of 2% by weight, which is uniformly dispersed in a composition having a solid content weight ratio of 30:70, and drying the coating layer at 100 ° C. Was produced. As shown in Table 1, it can be seen that the composite film has an insufficient drip-proof property.

[0128]

[Table 1]

[0129]

In the composite film of the present invention, since the fluororesin film and the fibrous resin film are laminated via the adhesive layer, the following excellent effects can be obtained.

First, the composite film of the present invention has an excellent drip-proof property and is also excellent in its durability.

Further, since the agricultural house coated with the composite film of the present invention can maintain the excellent drip-proof effect as it is, it cannot prevent the transmission of incident light.

Since the composite film of the present invention has the above-mentioned excellent properties, it can be used for packaging materials such as solar collectors, fruits and vegetables, coating materials for food freezers, etc.
It can be applied to a wide range of interior materials such as automobiles and houses.

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Claims (8)

[Claims] 1. A composite film comprising a fluororesin film and a fibrous resin film laminated on one surface of the fluororesin film via an adhesive layer. 2. The composite film according to claim 1, wherein an antifouling layer is provided on the outermost surface layer of the fluororesin film. 3. The composite film according to claim 1, wherein an ultraviolet absorbing layer is provided between the fluororesin film and the adhesive layer. 4. The composite film according to claim 3, wherein the ultraviolet absorbing layer comprises a composition containing an ultraviolet absorbing acrylic resin as a main component. 5. The composite film according to claim 2, wherein the antifouling layer is composed of a composition containing an inorganic hydrophilic colloid substance as a main component. 6. The composite film according to claim 1, wherein the adhesive layer and / or the ultraviolet absorbing layer is crosslinked. 7. The composite film according to claim 1, wherein the fluororesin film is composed of a composition containing an ethylene-4 fluoroethylene copolymer resin as a main component. 8. A farm house comprising the composite film according to any one of claims 1 to 7.