JP2816560B2 - Metallic film for exterior - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a decorative metal-finished film, in particular, to be adhered to an arbitrary object via an adhesive or a pressure-sensitive adhesive or by means such as heat lamination. Metal decorative film useful for giving a beautiful metallic decoration.

[Problems to be solved by conventional technology and invention]

Conventionally, a metal film for exterior, for example, a polyester film, an acrylic film, a metal layer is deposited and laminated by a method such as sputtering on a surface resin layer composed of a polyvinyl chloride film, etc. It is used for decorative purposes.

In a metal tone film prepared by using a polyester film as the surface resin layer, the adhesion between the metal layer and the polyester film is generally relatively good.
However, polyester resins themselves are not suitable for exterior applications because of their poor weather resistance, and have the drawback that polyester films are so hard that they have poor followability on curved surfaces and cannot be adhered to curved surfaces. Was.

Further, in the case of a metal-like film prepared using the above-mentioned acrylic resin film as the surface resin layer, the flexibility of the acrylic resin tends to decrease when the solvent resistance is improved. (Solvent) and excellent flexibility.

In addition, in a metal film for exterior made using a film made of a vinyl chloride resin as a surface resin layer, the film is weather-resistant, flexible, Although solvent resistance can be imparted, in this case, it is generally difficult to obtain close contact with the metal layer, and therefore, there has been a problem that the metal layer peels off, particularly when used outdoors. In this case, in outdoor use, the metal layer may be corroded or deteriorated by hydrochloric acid generated due to the deterioration of the vinyl chloride resin, so that a truly weather-resistant metal film for exterior can be obtained. It is not at present.

On the other hand, some attempts have been made to solve the above-mentioned disadvantages when using a vinyl chloride film.

For example, JP-A-58-42627 discloses that a cured film layer of a cationically polymerizable resin composition which is cured by irradiation with energy rays is provided on the surface of a vinyl chloride resin product, and metal deposition is performed on the surface of the film layer. There has been proposed a metal vapor deposition method for a vinyl chloride resin product, which is characterized by being applied. In addition,
JP-A-51-140965 proposes various resins as primer compositions for metal vacuum evaporation.

However, none of the above proposals are intended for outdoor use, and therefore no consideration is given to weather resistance. In addition, since no consideration was given to printability, the exterior metallized film prepared by the above-mentioned method was printed on the surface resin layer with ink clear, etc., and then dried. Had the disadvantage that fine cracks were generated. This is considered to be caused because the metal layer cannot follow the deformation of the surface resin layer due to heat or the like when heated for drying.

Further, in the case of manufacturing an exterior metal tone film in which a first intermediate layer is interposed between the surface resin layer and the metal layer, particularly when a flexible resin is used as the surface resin layer, the first intermediate layer or the metal In the manufacturing process of applying the layer, tension or heat is applied to the surface resin layer or the like or a solvent adheres to the surface resin layer in the process of being manufactured, and the surface resin layer is elongated or deformed, and as a result, There is also a problem that cracks are generated and sometimes the above-mentioned surface resin layer is torn, and therefore, it is difficult to stably produce a metal tone film for exterior use.

Therefore, an object of the present invention is to improve the adhesion between a surface resin layer formed of a polyvinyl chloride-based resin and a metal layer, and to prevent the corrosion and deterioration of the metal layer to eliminate the above-mentioned drawbacks. An excellent exterior that has sufficient weather resistance for exterior use and flexibility that can be attached to a curved surface, and has solvent resistance, hot water resistance, chemical resistance, etc., and is capable of various beautiful printing. To provide a metal tone film for use.

[Means for solving the problem]

As a result of various studies, the present inventors have found that a first intermediate layer is interposed between a surface resin layer (film) made of a vinyl chloride resin and a metal layer, and a second intermediate layer is deposited on the metal layer. It has been found that the above object is achieved by disposing the metal layer between the first intermediate layer and the second intermediate layer.

The present invention has been made based on the above findings. A metal layer is formed on a surface resin layer made of a polyvinyl chloride resin via a first intermediate layer, and a second layer is formed on the other surface of the metal layer. An intermediate layer is formed by adhesion, and the surface resin layer has a thickness of 20 to 200 μm and a total light transmittance of 3
0% or more, and a tensile strength at the time of 5% elongation of 2.0 kg / cm or less, the first intermediate layer has a thickness of 0.5 to 50 μm, and a total light transmittance of 30% or more. The second intermediate layer has a thickness of 0.5 to 50 µm and a thickness of 0.5 to 50 µm.

Next, the metallized film for exterior of the present invention will be described in detail.

In the present invention, the surface resin layer is formed of a vinyl chloride resin, and its thickness is adjusted to 20 μ to 200 μ, preferably 25 μ to 100 μ, more preferably 30 μ to 70 μ. When the thickness is less than 20 μm, the film is not easy to be torn due to low strength, and the sticking workability tends to deteriorate. On the other hand, when the thickness exceeds 200 μm, the flexibility of the surface resin layer tends to be lost and the cost is increased, which is not preferable.

The surface resin layer has a tensile strength at elongation of 5% of 2.
It is adjusted as a flexible film of 0 kg / cm or less. If the tensile strength at 5% elongation exceeds 2.0 kg / cm, it is not preferable because the suitability for sticking to a curved surface tends to be lost.

Further, the surface resin layer has a total light transmittance of 30% or more,
Preferably, it is adjusted to be 40% or more, more preferably 50% or more. If the total light transmittance is less than 30%, the metallic luster tends to be impaired, which is not preferable.

The vinyl chloride resin is not particularly limited as long as it is a resin composition containing a single vinyl chloride resin or a vinyl chloride resin containing a copolymer component as a resin component.
The resin composition may contain various additives such as a stabilizer, an antioxidant, an ultraviolet absorber, a modified resin, and a coloring agent, if necessary, as long as the above conditions are satisfied. Are preferred.

In addition, as the resin composition, a composition for molding a semi-rigid vinyl chloride resin having the following composition can be mentioned as a preferable example. (A) 100 parts by weight of a vinyl chloride resin containing 0 to about 20% by weight of a copolymer component, and (B) a liquid polyester plasticizer having a number average molecular weight (Mn) of about 1,500 or more in an amount of about 1 to about 1 And about 20 parts by weight, and 0 to about 10 parts by weight of another vinyl chloride resin plasticizer, and (C) a main chain composed of ethylene / vinyl ester of saturated carboxylic acid / carbon monoxide copolymer resin. A composition comprising an ethylene / vinyl ester resin having the formula (B) in an amount of about 45 to about 350% by weight based on the total amount of the plasticizer, and having a yield stress of 1 to 6 kg / mm ^2. Stuff.

In the above composition, the vinyl chloride resin (A) is not particularly limited, and may be appropriately selected and used as long as it is generally used for molding. The vinyl chloride resin may be a copolymer containing up to about 20% by weight, preferably about 10% by weight, particularly preferably up to about 6% by weight, in addition to a vinyl chloride homopolymer. There may be. As such a copolymer component, any vinyl monomer copolymerizable with a vinyl chloride monomer can be used without any particular limitation.

In the above composition, the plasticizer of (B) is the above (A)
About 1 to about 20 parts by weight, preferably about 1 to about 15 parts by weight, more preferably about 2 to 100 parts by weight of
From about 10 parts by weight of a liquid polyester plasticizer, and from 0 to about
10 parts by weight of another plasticizer for vinyl chloride resin. As the above liquid polyester plasticizer, number average molecular weight (Mn)
Is about 1,500 or more, preferably about 1,500 to about 6,000,
Preferably about 1,500 to about 4,000, more preferably about 2,000
~ About 4,000. Examples of the liquid polyester plasticizer include a liquid polyester derived from a dibasic acid having 4 to 15 carbon atoms and a dihydric alcohol having 2 to 20 carbon atoms. Among them, adipic acid, phthalic acid, Preferred examples include liquid polyesters derived from one or two selected from maleic acid and one to three selected from propylene glycol, dipropylene glycol, hexanediol, and butanediol. it can.

The plasticizer for vinyl chloride resin that can be used in combination is not particularly limited, and examples thereof include ordinary plasticizers such as phthalic acid esters and epoxy compounds.

In the composition, the ethylene / vinyl ester-based resin (C) is used in an amount of about 45 to about the total amount of the plasticizer (B).
It contains 350% by weight, preferably about 50 to about 300% by weight.

The copolymer resin (C) and its production method are known (for example, JP-B-55-50063; JP-A-48-26228).
Furthermore, it is available on the market (for example, trade name; Elvaloy, manufactured by DuPont, USA).

Examples of the vinyl ester used in the production of the resin (C) include vinyl acetate and propionate.

Further, in the composition, the yield stress is 1 to 6 kg / m
m ² , preferably 1-5 kg / mm ² , more preferably 1.2-4.5 k
a g / mm ^2.

A film made of a composition that satisfies each of the requirements described above, when a metal film for exterior use is prepared from the film, the metal material for exterior use such as printability, weather resistance, suitability for curved surface adhesion, and UV absorbent retention. It has various characteristics required as a film.

In the present invention, the first intermediate layer is formed of a urethane-based resin.

Examples of the urethane-based resin include polyurethane, polyurethane urea, a mixture of polyurethane and polyurethane urea, a mixture of polyurethane and / or polyurethane urea with another resin component, and a modified polyurethane and / or polyurethane urea.

Any of the above-mentioned polyurethane and polyurethane urea (hereinafter, also referred to as polyurethane or the like) can be used without any particular limitation. When both of them are used in combination, the mixing ratio can be arbitrarily changed.

Further, as the other resin component to be mixed with the polyurethane and / or polyurethane urea, phenol resin, furan resin, urea resin, melamine resin, guanamine resin, polyester resin, epoxy resin, silicon resin, polyimide resin, vinyl chloride resin, Vinylidene chloride resin,
Vinyl acetate resin, polyvinyl alcohol, polyvinyl acetal, alkyd resin, polystyrene, AS resin, ABS
Resins, AXS resins, methacrylic resins, acrylate resins, EVA resins, polyamides, cellulose resins, and petroleum resins.

Examples of the modified product such as the polyurethane include a graft polymer obtained by the action of a polymerization component (modified component), a mixture of the graft polymer and another component, or a reaction product. Examples of the polymerization component include alkyl (meth) acrylates, alkylamino (meth) acrylates, oxyalkyl phosphate (meth) acrylate,
Examples include vinyl monomers such as dicyclopentenyl (meth) acrylate, N-vinylpyrrolidone, acrylonitrile, styrene, acrylamide, vinyltoluene, and vinyl acetate.

When the modified product is a graft polymer, as other components to be mixed or reacted with the graft polymer, phenol resin, furan resin, urea resin, melamine resin, guanamine resin, polyester resin, epoxy resin, silicon resin, polyimide resin , Vinyl chloride resin,
Vinylidene chloride resin, vinyl acetate resin, polyvinyl alcohol, polyvinyl acetal, alkyd resin, polystyrene, AS resin, ABS resin, AXS resin, methacrylic resin,
Acrylic ester resins, EVA resins, polyamides, cellulose resins and petroleum resins can be mentioned.

Among the above modified products such as polyurethane, those particularly effective for forming the first intermediate layer include those comprising a graft polymer obtained by grafting polyurethane and / or polyurethane urea and an amino resin-based crosslinking agent. Further, there may be mentioned those in which the graft chain of the graft polymer is formed of a copolymer of a mixed monomer containing at least a hydroxyl group-containing α-β ethylene monomer and a carboxyl group-containing α-β ethylene monomer.

The urethane-based resin (modified product such as polyurethane) will be described in more detail. As the polyurethane and polyurethane urea constituting the graft polymer, polyester diols and diisocyanates generally used in the fields of paints, moldings, printing inks and the like are used. Can be used as a raw material, the molecular weight of which is 5,000 to 100,000,
It is preferably in the range of 8,000 to 50,000, and in order to smoothly carry out the graft reaction, 0.2 to 3 per molecule,
Those having 0.5 to 2 α-β ethylenically unsaturated bonds are preferred.

As a method for introducing an α-β ethylenically unsaturated bond into the polyurethane, as an intermediate material, when synthesizing a polyester diol, an appropriate amount of maleic acid, itaconic acid or the like is condensed as a part of the material. Methods can be mentioned.

As the polyol used in the production of the polyurethane, the polyester having the α-β ethylenically unsaturated bond, polyester diol containing no α-β ethylenically unsaturated bond, polycaprolactone diol, polyether diol, polycarbonate Other bifunctional alcohols such as diol, ethylene glycol, propylene glycol, butanediol, hexanediol, cyclohexanedimethanol, neopentyl glycol, etc. may be mixed and used. Further, when it is desired to increase the molecular weight, tri- or higher-functional alcohols such as trimethylolpropane, trimethylolethane, and pentaerythritol may be partially used. However, it is needless to say that the amount needs to be set within a technically allowable range in consideration of gelation by three-dimensional formation.

Examples of the isocyanate used in the production of the polyurethane include generally used diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate, and these may be used alone or in combination of two or more. Can be used.

Further, polyurethane urea is obtained by synthesizing a terminal isocyanate group-containing prepolymer by one or more of the above-mentioned polyol compounds exemplified as the raw materials for synthesizing the polyurethane and one or more raw materials of the polyisocyanate according to a conventional method. The prepolymer can be obtained by conducting a chain elongation degree reaction with a diamine having two primary and / or secondary amino groups in one molecule according to a conventional method.

As the diamine, for example, ethylene diamine,
Examples thereof include propylene diamine, hexamethylene diamine, piperazine, isophorone diamine, and cyclohexyl methane diamine.

In the case of producing any of polyurethane and polyurethane urea, monoalcohols such as methanol, ethanol and propanol, monoamines such as diethylamine, dipropylamine and dibutylamine, monoethanolamine, diethanolamine, monopropanolamine and dipropanolamine And the like can also be used as a chain elongation terminator.

Next, the graft chain constituting the graft polymer will be described. As the hydroxyl group-containing α-β ethylene-based monomer contained in the mixed monomer used for the synthesis of the graft chain, hydroxyethyl (meth) acrylate, hydroxypropyl ( Hydroxyalkyl (meth) acrylates such as meth) acrylate; caprolactone modified products of these hydroxyalkyl (meth) acrylates (trade name: Praxel FM series manufactured by Daicel Chemical Industries, Ltd.); polyether diol (meth) acrylic acid Esters, that is, hydroxy polyalkyl ether glycol mono (meth) acrylate, and the like can be given.

The hydroxyl group-containing α-β ethylene monomer is desirably contained in the mixed monomer in an amount of 5 to 80 mol%, preferably 10 to 50 mol% in order to homogenize a crosslinked structure described in detail below. .

Further, as the carboxyl group-containing α-β ethylene-based monomer contained in the mixed monomer, acrylic acid,
Examples include methacrylic acid, maleic acid, itaconic acid, crotonic acid and the like.

In addition, the carboxyl group-containing α-β ethylene-based monomer improves the compatibility with the crosslinking agent and, from the viewpoint of forming a uniform clear film, from 1 to 40 to the mixed monomer.
It is desirable that the content be in the range of 2 mol%, preferably 2 to 20 mol%.

Further, in addition to the above-mentioned two essential monomers, the above-mentioned mixed monomer includes monomers commonly used in the production of an acrylic copolymer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Alkyl (meth) such as butyl (meth) acrylate
Acrylates, alkylamino (meth) acrylates such as dimethylaminoethyl (meth) acrylate, oxyalkyl (meth) acrylate phosphate, dicyclopentenyl (meth) acrylate, N-vinylpyrrolizone, acrylonitrile, styrene, acrylamide, vinyl Toluene, vinyl acetate and the like may be mixed as necessary.

The mixed monomer to be reacted with the polyurethane or the like is preferably up to 1: 1 from the viewpoint of maintaining the toughness of the coating film. However, if the amount is too small, the compatibility with the cross-linking agent is reduced and the formation of the clear film is hindered. Therefore, the amount of the mixed monomer is 2 parts by weight or more, preferably 4 parts by weight, based on 100 parts by weight of the polyurethane or the like. It is preferable that it is above.

The grafting reaction of the polyurethane or the like can be carried out by causing a mixed system of the polyurethane or the like and the mixed monomer to carry out polymerization in the presence of a reaction catalyst. Examples of the reaction catalyst that can be used at that time include those used in a usual radical polymerization reaction such as azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide and cumene hydroperoxide.

In producing the urethane-based resin, when producing the above-mentioned polyurethane, polyurethane urea, and graft polymer used as an intermediate material,
It goes without saying that the viscosity can be adjusted to an appropriate value by using one or more organic solvents.

Amino resins such as melamine resins, benzoguanamine resins, and urea resins are subjected to treatment such as methylolation, methoxylation, and butoxylation as amino resin-based crosslinking agents used together with the graft polymer to form the urethane-based resin. Amino resin derivatives.

The mixing ratio of the graft polymer and the amino resin-based crosslinking agent is, from the viewpoint of maintaining a balance between improvement in water resistance and toughness of the coating film, with respect to 100 parts by weight of the graft polymer, the crosslinking agent 5 to 60. Parts by weight, more preferably 10-40
Desirably, parts by weight are used.

When adjusting the urethane-based resin, in addition to the graft polymer and the cross-linking agent, a diluting solvent, a leveling agent, a thixotropic agent, and the like, which are generally used in a coating technology field, are added. Needless to say, it can be adjusted by adding a curing catalyst, a dye, a pigment, and the like.

The method for forming the first intermediate layer in the metal film for exterior of the present invention with the urethane-based resin described in detail above is not particularly limited, and the urethane-based resin is made into a solution, and a desired component is further added. The polymer solution is adjusted by spraying, curtain flow coating, roll coater coating, doctor knife coating, dip coating, flow coating, brush coating and the like.

By forming the first intermediate layer with a urethane-based resin as described above, protection of the metal layer described later, sufficient fixing and adhesion of the metal layer, and obtaining long-term weather resistance as a metal-like film Becomes possible.

The thickness of the first intermediate layer is 0.5 to 50μ, preferably 1 to 3
It is adjusted to 0 μ, more preferably 2 μ to 20 μ. When the thickness of the first intermediate layer is less than 0.5μ, it is difficult to fix the metal layer, and further, the metal layer is protected from hydrochloric acid or the like caused by deterioration of the vinyl chloride resin, and from the vinyl chloride resin. Transfer of a compounding agent or the like from a film (hereinafter, also referred to as a vinyl chloride film) cannot be effectively prevented.
Further, when the thickness is 50 μm or more, the cost is increased, which is not preferable, as well as a problem that the flexibility of the vinyl chloride film is impaired. The first intermediate layer preferably has a pencil hardness of B to 2H so as not to impair the flexibility of the vinyl chloride-based film and to sufficiently hold and fix the metal layer.

The first intermediate layer has a total light transmittance adjusted to 30% or more. If the total light transmittance is less than 30%, the metallic luster tends to be lost, which is not preferred. Further, the first intermediate layer can be crosslinked as required, and various compounding agents can be added to the first intermediate layer within a range satisfying the conditions such as the light transmittance. Examples of the compounding agents include coloring agents such as general pigments, pearl pigments and metal foils, ultraviolet absorbers, stabilizers, coupling agents, antioxidants, modifiers and the like.

In the present invention, the metal layer may be formed of the following metal, and the thickness thereof is 50 to 2,000, preferably 100 to 1,000, and more preferably 300 to 600, although it depends on the metal used. The thickness of the above metal layer is 50
ÅIf it is thinner, the concealment of the metal layer is not sufficient,
On the other hand, if the thickness exceeds 2,000 mm, cracks tend to occur in the metal layer, and the cost is also increased.

In the present invention, the method for applying the metal layer does not include a method for bonding a metal foil using an adhesive, but applies the method using a vapor deposition method, a sputtering method, or a plasma method. The metal that forms the metal layer of the present invention is not particularly limited, and examples thereof include metals such as aluminum, gold, silver, copper, nickel, chromium, magnesium, and zinc. Aluminum, chromium or nickel is preferable in consideration of easiness, durability and the like, and it is particularly preferable to use chromium excellent in corrosiveness.
The metal layer may be formed of an alloy composed of two or more metals.

In the present invention, the first intermediate layer can be formed of an acrylic resin, a urethane resin, or various other resins, and among them, an acrylic resin is preferable.

As the acrylic resin, for example, at least 50
Suitable examples include those containing as a component at least 80% by weight, preferably at least 80% by weight of a polyacrylate and / or polymethacrylate.

Examples of the polyacrylate include those obtained by polymerizing ethyl acrylate, methyl acrylate, propyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, 2-ethylhexyl acrylate and the like as monomers, and Examples of the polymethacrylate include those obtained by polymerizing methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, or the like as a monomer.

As components other than the above both polymers, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, urethane resin, epoxy resin, vinyl chloride-ethylene copolymer, etc. can be used.

The method for forming the second intermediate layer is not particularly limited.For example, a polymer solution is prepared by dissolving components such as the polyacrylate in advance, and the polymer solution is the same as in the case of the first intermediate layer. In a method, it can be formed by coating the other side of the metal layer and then drying to remove the solvent.

As described above, when the acrylic resin is used as a component and the content thereof is 50% by weight or more, the metal layer can be protected and sufficiently fixed. If the amount is less than 50% by weight, these effects cannot be sufficiently obtained.

The thickness of the second intermediate layer is 0.5 to 30μ, preferably 1 to 2
It is adjusted to 0 μ, more preferably 2 to 15 μ. If the thickness of the second intermediate layer is less than 0.5 μm, it is difficult to protect and fix the metal layer, and furthermore, it is necessary to prevent intrusion of moisture from an adhesive (adhesive) layer, which will be laminated as needed, which will be described later. It is not preferable for prevention. On the other hand, if the thickness is more than 30 μm, the cost is increased, which is not preferable. The second intermediate layer preferably has a pencil hardness of B to 3H so as not to impair flexibility and to sufficiently hold and fix the metal layer.

The second intermediate layer can be crosslinked as required, and various binders can be added to the intermediate layer as long as the above conditions are satisfied. Examples of the compounding agent include coloring agents such as general pigments, pearl pigments and metal foils, ultraviolet absorbers, stabilizers, and modifiers.

Usually, the metallized film for exterior of the present invention, after forming the second intermediate layer as described above, forming an adhesive layer or an adhesive layer on the second intermediate layer, further forming the adhesive layer. It is completed by sticking release paper to layers and the like. The exterior metallic film is used by being bonded to a desired adherend via the above-mentioned pressure-sensitive adhesive layer or adhesive layer.
The pressure-sensitive adhesive layer or the adhesive layer is not particularly limited,
It is preferable to use an acrylic adhesive, which is also an acrylic adhesive or adhesive having good water resistance.

The metal film for exterior of the present invention is not necessarily limited to the above-mentioned one having the pressure-sensitive adhesive layer or the adhesive layer formed thereon, and may have a structure to be adhered by other means such as heat lamination. Good.

Next, an example of a method for manufacturing an exterior metal tone film suitable for producing the exterior metal tone film of the present invention will be described.

The metal film for exterior of the present invention can be easily and reliably manufactured by the following method.

That is, first, a support film is prepared, and a surface resin layer is formed on one surface of the support film. The support film is not particularly limited as long as the film is made of a material that can withstand the manufacturing conditions such as tension, heat, and solvent in each manufacturing process. Although what is generally called process paper can be used, a polyester film is preferred from the viewpoint of surface smoothness and thickness accuracy.

The method for forming the surface resin layer is not particularly limited, and examples thereof include a spray method, a printing method, and a coating method. Coating methods are preferred.

Next, a first intermediate layer made of, for example, a urethane resin is formed on the surface resin layer formed on the support film. The method for forming the first intermediate layer is also not particularly limited, and a spray method as in the case of the surface resin layer,
A printing method, a coating method, or the like can be employed, and in some cases, a heat lamination method can be employed.

Further, a metal layer is formed on the first intermediate layer formed on the surface resin layer. As described above, a vacuum evaporation method, a sputtering method, and a plasma method are employed for forming the metal layer.

After forming the metal layer as described above, a second intermediate layer made of, for example, an acrylic resin is formed on the other surface of the metal layer. The deposition can be performed, for example, in the same manner as in the case of the first intermediate layer. Thereafter, the support film is peeled off from the surface resin layer to form the exterior metallized film of the present invention. In addition, for example, until the subsequent steps such as a step of laminating the pressure-sensitive adhesive and the adhesive on the exterior metal tone film and further laminating a release paper, various treatments are performed without peeling the exterior metal tone film from the support film. It goes without saying that this may be done.

According to the manufacturing method described above, the supporting film functions as a fixing carrier for each layer of the metal tone film in each step, and also functions as a protective layer for the surface resin layer. In addition to the reliable production, it is possible to effectively prevent the surface from being damaged by an external factor in each step.

In the above-described manufacturing method, a step of forming another layer such as a surface coat layer can be added as necessary.

〔Example〕

Next, the metal film for exterior of the present invention will be described in more detail with reference to Reference Examples and Examples.

First, prior to the description of the examples, test methods performed in reference examples, examples, and comparative examples described later will be described.
The reference example is substantially the same as the exterior metal film of the present invention except that the second intermediate layer is not provided.

Total light transmittance The total light transmittance was measured using a direct reading haze meter (manufactured by Toyo Seiki Seisaku-sho, Ltd.) in accordance with the measurement of parallel light transmittance according to JIS-K-6714.

Tensile test (Measurement of tensile strength at 5% elongation) According to JIS-K-6734, a sample film was cut into a predetermined shape to prepare a sample for a tensile test, and the sample was subjected to a temperature of 23 ± 2 ° C and a relative humidity of 50 ±. 5% environment, pulling speed 200mm / min., Pulling interval 100mm, chart speed 500
A tensile test was performed using a tensile tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.) under the conditions of mm / min. The strength at an elongation of 5% was read from the chart at that time and taken as the tensile strength at 5% elongation.

Heat resistance The metal film for exterior was cut into 50 mm x 50 mm, and after peeling off the release paper, it was stuck on an alkyd melamine coated plate (manufactured by Nippon Test Panel Industry Co., Ltd.) using a squeegee. Next, this was left at room temperature for 72 hours, and then left gently in a circulating hot air dryer set at 80 ° C. ± 2 ° C. for 168 hours to perform a heat treatment. After the above heat treatment, the panel is taken out, the state of cracks in the film is observed, and
・ Evaluation was made in three stages of Δ · ×.

…: There is no crack on the film surface and the film has a mirror surface.

Δ: Cracks are observed in a part of the film surface.

C: Cracks are present on the film surface and the mirror surface is lost.

Applicability to curved surface Metallic film for exterior use is attached using the curved surface of the bottom of a stainless steel ball with a diameter of 180 mm, and a metal exterior film with a diameter of several mm can be attached without causing wrinkles. It was evaluated according to the following. For the evaluation method, the maximum diameter value that could be stuck without wrinkles was taken as the curved surface sticking suitability value.

Adhesion of the (first) intermediate layer to the surface resin layer An adhesive layer is formed on the film before metal deposition, and it is adhered to an aluminum plate and immersed in hot water at 80 ° C for 4 hours. After taking out from the inside and leaving it at room temperature for 24 hours, the adhesion between the surface resin layer and the (first) intermediate layer is checked by trying to separate them with a single blade razor blade.・ · × was evaluated.

…: The surface resin layer and the (first) intermediate layer are completely adhered.

X: The surface resin layer and the (first) intermediate layer are separated.

Adhesiveness of metal layer A cellophane tape was pressure-bonded to the metal layer side of the test piece in a stage before the adhesive layer (or adhesive layer) or the second intermediate layer was formed by adhesion, and the cellophane tape was vigorously peeled off. The state of peeling of the metal layer at this time was observed, and evaluated by the following contents.

…: The metal layer does not peel off.

×: The metal layer is peeled off even at a part.

Warm water resistance Warm water resistance (1): The film before metal layer deposition was immersed in warm water of 40 ° C. for 168 hours, and evaluated according to the following three grades of ○, Δ, and × according to the degree of whitening of the film at that time. .

…: No abnormality △: Very thin whitening has occurred on the entire surface or a part of the film.

X: Whitening has occurred on the entire surface of the film.

Warm water resistance (2): After cutting the metal film for exterior to 50 mm x 50 mm, peeling off the release paper, and using a squeegee, alkyd melamine coated plate (manufactured by Nippon Test Panel Industry Co., Ltd.)
Pasted on. Then leave it at room temperature for 72 hours, then
The sample was immersed in warm water of 8 ° C. for 8 hours and evaluated according to the same criteria.

Solvent resistance (1) Gasoline resistance: 50mm x 50mm metal exterior film
After peeling off the release paper, alkyd melamine coated plate using a squeegee (Nippon Test Panel Kogyo Co., Ltd.)
Made). Next, this was left at room temperature for 72 hours, immersed in gasoline at 20 ° C. for 30 minutes, and evaluated by the following three grades of ○, Δ, and × according to the appearance of the film at that time.

…: No abnormality Δ: Cracks have occurred in a part of the film.

X: Cracks are formed on the entire surface of the film.

(2) Methanol resistance: Metallic film for exterior 50mm x 50
mm, peel off the release paper and use an alkyd melamine coated plate (Nippon Test Panel Kogyo Co., Ltd.) using a squeegee.
Made). Next, after leaving this at room temperature for 72 hours, it was immersed in methanol at 20 ° C. for 10 minutes, and the appearance of the film at that time was evaluated according to the following three grades of △, Δ, and ×.

…: No abnormalities…: The mirror surface of the edge portion of the film is lost.

X: The mirror surface of the entire surface of the film is lost.

Chemical resistance (1) Acid resistance: After cutting the metal film for exterior to 50 mm x 50 mm, peeling off the release paper, and using a squeegee on an alkyd melamine coated plate (manufactured by Nippon Test Panel Industry Co., Ltd.) Pasted on. Next, leave it at room temperature for 72 hours,
It was immersed in an aqueous solution of PM in H ₂ SO ₃ at room temperature for 14 days, and the appearance of the film at that time was evaluated in the following three grades of △, Δ, and ×.

○: No abnormality △: Metal corrosion occurred only at the edge of the film.

X: Corrosion of metal has occurred on the entire surface of the film.

(2) Salt water resistance: After cutting the metal film for exterior to 50 mm x 50 mm, peeling off the release paper, and using a squeegee, alkyd melamine coated plate (manufactured by Nippon Test Panel Industry Co., Ltd.)
Pasted on. Then, leave it at room temperature for 72 hours,
The film was immersed in a 1% aqueous solution of NaCl at room temperature for one month, and the appearance of the film at that time was evaluated according to the following three grades of △, Δ, and ×.

○: No abnormality △: Metal corrosion occurred only at the edge of the film.

X: Corrosion of metal has occurred on the entire surface of the film.

(QVA) Weather resistance (1): Metallic film for exterior is made of aluminum plate (17 ×
35mm), leave it at room temperature, and then apply it to QUV (Th
eQ-Panel Company).

The exposure conditions at this time were UV at a black panel temperature of 60 ° C.
One cycle was 8 hours of light irradiation and 4 hours of dew condensation at a black panel temperature of 50 ° C.

The evaluation was performed at 300 hours and 700 hours, compared to the standard sample (surface resin layer), with
It was evaluated on a scale.

…: No abnormalities…: The mirror surface of the edge portion of the film is lost.

X: The mirror surface of the entire surface of the film is lost.

Weather resistance (2): Except that the exposure condition was set to a black panel temperature of 70 ° C. It is almost the same as the case of the weather resistance (1).

Reference Example 1 First, a film having a thickness of 40 μm was prepared by a casting method using a resin composition having the following basic composition, and was used as a surface resin layer of a metal-finish film for exterior use. This film had a tensile strength at 5% elongation of 1.5 kg / cm and a total light transmittance of 89%. In addition, as shown later, the subsequent steps are performed in a state where the above-mentioned film is adhered to the supporting film.

Basic composition Vinyl chloride resin 100 Ethylene / vinyl ester resin 25 Polyester plasticizer 10 The vinyl chloride resin is Nicavinyl SG-11
00N (manufactured by Nippon Carbide Industrial Co., Ltd.), Elvaloy was used as the ethylene / vinyl ester resin, and a mixed dihydric alcohol consisting of propylene glycol, butanediol and hexanediol as the polyester plasticizer and adipic acid were used. The one having a number average molecular weight (Mn) of about 3000 synthesized from was used. Further, the production of the film by the casting method was specifically performed as follows.

Tetrahydrofuran was added so that the resin concentration of the mixed resin component became 20% by weight, and the mixture was stirred and dissolved in a closed container at 100 ° C. for 2 hours to obtain a resin solution composition.

Then, after cooling and defoaming the above resin solution composition, it is cast on a polyester film (support film) using a caster, dried with hot air at 140 ° C. for 15 minutes, and the surface adhered to the support film. A film constituting the resin layer was prepared.

Next, the following polyurethane (urethane resin) solution is
Using a screen printing machine (trade name: Minomat 600L, manufactured by Mino Group), using a 180-mesh monotetron screen, coat one surface of the film constituting the surface resin layer, and then adjust the temperature to 120 ° C ± 3 ° C. Drying was performed in an oven for 60 minutes to form an intermediate layer having a thickness of 10 μm. The total light transmittance of this intermediate layer was 88%. In addition, as the above-mentioned polyurethane solution, trade name: Vernock L7-
920 (Dai Nippon Ink Chemical Co., Ltd., non-volatile content 25 ± 1)
%, Solvent toluene, secondary butanol, viscosity Z ₁ ~
Z ₄₎ was used.

Next, after a metal layer is formed to a thickness of about 500 mm by performing aluminum vapor deposition on the surface of the intermediate layer, an acrylic adhesive (trade name: PE-121, Nippon Carbide Industry Co., Ltd.) is applied to the surface of the metal layer. 100 parts by weight and a crosslinking agent (trade name: Coronate L)
・ Nippon Polyurethane Industry Co., Ltd.) 1 part by weight of the mixed solution is applied and dried to form an adhesive layer having a thickness of about 35 μ, and a silicone-coated release paper is applied to the applied surface of the adhesive layer. After the combination, the supporting film made of polyester was peeled off to prepare a metal-tone sheet for exterior use.

As shown schematically in the partial cross-sectional view of FIG. 2, the thus produced exterior metal tone film has an intermediate layer 2a, a metal layer 3, an adhesive layer 5 and a release paper on the surface resin layer shown in FIG. 6 are sequentially laminated.

Table 1 below shows the results of the evaluation of each of the above test items performed on the metal film for exterior of Reference Example 1 together with the results of Reference Examples 2 to 4 and Example 1 described below.

For comparison, the results of the case of using only the surface resin layer (Comparative Example 1 described later) are also shown.

[Reference Example 2] The structure, dimensions, manufacturing method, and the like of the exterior metal tone film of Reference Example 2 are substantially the same as those of Example 1 except that the intermediate layer is formed of the following urethane-based resin.

The urethane-based resin in Reference Example 2 is a graft polymer obtained by grafting the following polyurethane resin with an acrylic monomer. That is, used in Reference Example 1 above,
Trade name: Invariant color acrylic grafted urethane lacquer obtained by using Barnock L7-920 as a base urethane and grafting a mixed monomer containing at least a hydroxyl group-containing α-β ethylene monomer and a carboxyl group-containing α-β ethylene monomer.・ Product Name: Burnock L8
−971 (Dai Nippon Ink Chemical Industry Co., Ltd., nonvolatile content 25 ±
1%, solvent toluene, DMF). The total light transmittance of the intermediate layer formed of the urethane-based resin was 88%.

REFERENCE EXAMPLE 3 The structure, dimensions, manufacturing method, and the like of the exterior metal tone film of Reference Example 3 are substantially the same as those of Reference Example 1 except that the intermediate layer is formed of the following urethane-based resin.

The urethane resin in Reference Example 3 is a urethane resin.
The basic composition is 100 parts by weight and 25 parts by weight of a crosslinking agent. Here, as the urethane resin, the trade name: Vernock L7-920 used in Reference Example 1, and
As a cross-linking agent, butylated melamine resin, trade name: Super Beckamine J-820-60 (Dainippon Ink Industries, Ltd.)
Manufactured, 60% non-volatile content, solvent xylene, n-butanol, viscosity Q to T). The total light transmittance of the intermediate layer formed of the urethane-based resin was 88%.

[Reference Example 4] The structure, dimensions, manufacturing method, and the like of the exterior metal tone film of Reference Example 4 are substantially the same as those of Reference Example 1, except that the intermediate layer is formed of the following urethane-based resin.

The urethane-based resin in Reference Example 4 is basically composed of 100 parts by weight of the grafted polyurethane resin and 25 parts by weight of the crosslinking agent. Here, as the above-mentioned grafted polyurethane, the brand name used in Reference Example 2 was:
Burnock L8-971 was used, and as a cross-linking agent, the butylated melamine resin used in Reference Example 3 and trade name: Super Beckamine J-820-60 was used. The total light transmittance of the intermediate layer formed of the urethane-based resin was 88%.

[Example 1] The metal film for exterior of Example 1 is the same as that of Reference Example 4 described above.
The metallized film for exterior has a structure in which a second intermediate layer made of an acrylic resin is further adhered to the other surface of the metal layer 3 and the metal layer 3 is backed. The outline is
As shown in the partial cross-sectional view of FIG. 1, except that the second intermediate layer 4 is adhered and formed on the other surface of the metal layer 3, the same configuration as the exterior metal tone film shown in FIG. The intermediate layer 2a in FIG. 2 corresponds to the first intermediate layer 2 in FIG.

After forming the metal layer 3 in the same manner as in the case of the reference example 4, the second intermediate layer 4 is applied with the following polymer solution containing an acrylic resin in the same manner as in the case of the intermediate layer in the reference example 1. The other surface of the metal layer was coated on a screen printing machine (trade name: Minomat 600L, manufactured by Mino Group) using a 180 mesh monotetron screen.
Then, drying was performed in an oven adjusted to 65 ± 3 ° C. for 60 minutes to form an intermediate layer having a thickness of 10 μm. The second intermediate layer had a total light transmittance of 88%.

The polymer solution for forming the second intermediate layer 4 is composed of 58% by weight of methyl methacrylate and 30% by weight of butyl acrylate.
And a xylene solution containing 48% of a resin component having a composition of 12% by weight of 2-hydroxyethyl methacrylate.
0 parts by weight, Coronate EH (Nippon Urethane Industry) 1
4 parts by weight were added, sufficiently stirred, and mixed to prepare.

When the adhesion between the metal layer 3 and the second intermediate layer 4 was evaluated by the same method as described in the above-mentioned section "Adhesion of (first) intermediate layer to surface resin layer", it was extremely good. .

Comparative Example 1 An exterior metallized film of Comparative Example 1 was prepared in the same manner as in Reference Example 1 except that the metal layer 3 was directly formed on the surface resin layer 1 without forming the intermediate layer 2a. Created.

From Table 1 above, each of the metallized films for exterior use of Reference Examples 1 to 4 is superior to the metallized film for exterior use of Comparative Example 1 in various properties. It turns out that it is even better than the metal-tone film for exterior of No. 1.

〔The invention's effect〕

The metallized film for exterior of the present invention has good adhesion of the metal layer, and can be pasted on a curved surface, and furthermore, various beautiful prints can be made on the surface resin layer, and the metal layer can be printed over time. It does not cause corrosion and deterioration, has excellent weather resistance, and also has excellent hot water resistance, solvent resistance, and chemical resistance.

[Brief description of the drawings]

FIG. 1 is a schematic partial cross-sectional view of an exterior metallized film of Example 1, and FIG. 2 is a schematic partial cross-sectional view of an exterior metallized film of Reference Example 1. 1; surface resin layer, 2; first intermediate layer 3; metal layer, 4; second intermediate layer

Claims (3)

(57) [Claims] 1. A metal layer is formed on a surface resin layer made of a polyvinyl chloride resin via a first intermediate layer formed of a urethane resin, and a metal layer is formed on the other surface of the metal layer. Two intermediate layers are formed by adhesion, and the surface resin layer has a thickness of 20 to 200 μm and a total light transmittance of 30.
% Or more, and the tensile speed at the time of 5% elongation is 2.0 kg / cm or less. The first intermediate layer has a thickness of 0.5 to 50 μm and a total light transmittance of 30%.
% Or more, wherein the metal layer has a thickness of 50 to 2000 mm, and the second intermediate layer has a thickness of 0.5 to 50 µm. 2. The metal film for exterior use according to claim 1, wherein said second intermediate layer is formed of an acrylic resin. 3. The urethane resin constituting the first intermediate layer comprises a graft polymer obtained by grafting polyurethane and / or polyurethane urea and an amino resin-based crosslinker, and the graft chain of the graft polymer has at least The acrylic resin constituting the second intermediate layer is formed of a copolymer of a mixed monomer containing a hydroxyl group-containing α-β ethylene monomer and a carboxyl group-containing α-β ethylene monomer. The metal film for exterior use according to claim 1, further comprising acrylate and / or polymethacrylate as a component.