JPH10138423A - Composite film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite film containing a thermoplastic polyester film and a polyolefin film as main materials. SOLUTION: This composite film is a film wherein a resin composition layer (a) comprising 10-70wt.% of an amorphous polyolefin in which the content of propylene and/or butene -1 is at least 50wt.%, and 90-30wt.% of a crystalline polypropylene, and a layer (b) comprising a crystalline polypropylene are laminated in at least three layers. Moreover, a multilayer film (A), both outer layers of which are formed of the (b) layer, and a thermoplastic polyester film (B) having a thermally adhesive layer on at least one face thereof are laminated on each other with the thermally adhesive layer of the film (B) therebetween.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet film material used for building materials and furniture.
The present invention relates to a composite film mainly composed of a thermoplastic polyester film and a polyolefin film.

[0002]

2. Description of the Related Art Conventionally, building materials, especially ceiling materials, interior materials such as wallpaper, furniture, especially kitchen furniture such as sinks, countertops, cupboards, tables, system kitchen doors, office shelves such as bookshelves and cabinet members. As a surface decorative sheet for furniture or the like, a vinyl chloride (PVC) sheet or a sheet obtained by laminating a coating layer or a film on the surface has been used. However, this PVC film is excellent in design and cost performance, but has solvent resistance,
Not only are the performances such as chemical resistance and stain resistance insufficient, but the use of this chlorine-containing resin tends to be avoided due to recent social demands for global environmental protection. Therefore, it is non-chlorine and has excellent solvent resistance, chemical resistance, and printability.
The use of economical biaxially oriented PET films has been considered. However, this PET film has a number of problems, such as the need to apply an adhesive offline and then laminate by a method such as dry lamination when finishing a decorative sheet by laminating several films. there were.

As an alternative to PVC, economical olefin materials that are non-chlorine and have excellent solvent resistance, chemical resistance and stain resistance have been studied. Not only is there a problem with the surface properties, but it is a relatively soft material, so the surface is easily scratched (poor in abrasion resistance), and is not suitable for printing for design processing or coating for surface processing And the like.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a film for a decorative sheet having a novel structure which combines the properties of a thermoplastic polyester film with the advantages of a polyolefin resin film. As a result of intensive studies, a design is obtained by using a polyolefin resin multilayer film with a specific composition and composition as a base material, and using a thermoplastic polyester film with a large surface hardness as a surface material, and heating and laminating these with a thermal adhesive layer. This led to the development of a chlorine-free composite film for decorative sheets that is excellent in water resistance, solvent resistance, stain resistance, secondary workability, and economy.

[0005]

That is, the gist of the present invention is that the content of propylene and / or butene-1 component is 50%.
10% to 70% by weight of amorphous polyolefin of 10% by weight or more
And a resin composition layer (a) composed of 90 to 30% by weight of crystalline polypropylene, and a layer (b) composed of crystalline polypropylene are a film laminated at least in three layers, and both outer layers are (b) A composite formed by laminating a multilayer film (A) composed of layers and a film (B) composed of a thermoplastic polyester film having a thermal adhesive layer on at least one surface via the thermal adhesive layer Film. In addition, the composite film of the present invention,
The thickness of the various films or layers constituting it is not particularly limited, and within the range of commonly used terms, even if "film" is replaced with "sheet", the effect of the present invention is the same. Therefore, the term “film” in the present specification includes all sheets.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, the amorphous polyolefin (hereinafter, referred to as “amorphous polyolefin”) used in the layer (a) is an amorphous polyolefin having a propylene and / or butene-1 content of 50% by weight or more. Any quality olefin polymer may be used. For example, amorphous polypropylene or polybutene-1 or a copolymer of propylene or butene-1 with another α-olefin can be used. If the content of the propylene and / or butene-1 component in the amorphous polyolefin is less than 50% by weight, the compatibility with the crystalline polypropylene is undesirably reduced.

The above-mentioned amorphous polyolefin refers to boiling n-
Heptane insoluble content, that is, Soxhlet extracted insoluble content with boiling n-heptane is 70% by weight or less, preferably 6% by weight.
0% by weight or less. If the boiling n-heptane-insoluble content is more than 70% by weight, the ratio of the amorphous portion becomes small, and the desired flexibility cannot be imparted to the obtained film. Further, the above-mentioned amorphous polyolefin of the layer (a) preferably has a number average molecular weight of 1,000.
0 to 200,000, preferably 1,200 to 100,
000, and more preferably 1,500 to 20,000. When the number average molecular weight exceeds 200,000, film formation is difficult, and when it is less than 1,000, the mechanical strength decreases. In the present invention, the amorphous polyolefin is
One type or a combination of two or more types can be used.

As the amorphous polypropylene, atactic polypropylene produced as a by-product during the production of crystalline polypropylene may be used, or it may be used as it is produced from raw materials. At this time, a copolymer of propylene or butene-1 and another α-olefin can be produced from a raw material so as to contain a predetermined propylene or butene-1 component and used. In addition, when producing for the purpose, for example,
It can be obtained by polymerizing a raw material monomer in the presence of hydrogen or in the absence of hydrogen using a titanium-supported catalyst supported on magnesium chloride and triethylaluminum. From the viewpoint of stability of raw material supply and stability of quality,
It is preferred to use the desired amorphous polyolefin produced for the purpose. Also, if there are applicable suitable commercial products,
A commercially available product can be appropriately selected and used.

In the present invention, as the amorphous polyolefin of the layer (a), specifically, polypropylene, propylene, ethylene copolymer and propylene / butene-1 copolymer having predetermined characteristics such as the above-mentioned propylene component content are used. Polymer, propylene / butene-1 / ethylene-3 terpolymer, propylene / hexene-1 / octene-1 / 3 terpolymer, propylene / hexene-1 / 4-methylpentene-1 / 3 terpolymer Amorphous polyolefins whose main component is a propylene component such as coalescence are mentioned. Polybutene-1, butene-1 / ethylene copolymer, butene-1 / propylene copolymer, butene-1 / propylene / ethylene terpolymer having predetermined properties such as the above butene-1 component content Butene-1, hexene-1, octene-1, terpolymer, butene-1, hexene-1, 4-
Amorphous polyolefins having a butene-1 component as a main component, such as methylpentene-1-ternary copolymer, may also be mentioned.
When the amorphous polyolefin is a propylene / ethylene copolymer, the ethylene component content is 0 to 30% by weight,
Preferably 1 to 20% by weight is desirable. When the ethylene content is more than 30% by weight, the obtained film becomes too soft.

In the present invention, when the amorphous polyolefin in the layer (a) is a propylene / butene-1 copolymer, a copolymer mainly composed of propylene and a copolymer mainly composed of butene-1 are used. And a copolymer containing propylene and butene-1 as main components. It is desirable that the content of these main components is 50% by weight or more and the remaining components are less than 50% by weight, preferably 1 to 45% by weight, more preferably 5 to 44% by weight. The propylene / butene-1 copolymer has high tensile elongation, high rebound resilience, and high cohesion, and can be optionally used as an amorphous polyolefin for the (a) layer. Specifically, for example, Lexene of the United States
Commercially available products such as REXTAC (REXTAC) and "Bestplast" from Huls (Germany) can be used.

In the present invention, the crystalline polypropylene used in the layer (a) includes polypropylene which is generally commercially available for extrusion molding, injection molding, blow molding and the like, and is insoluble in boiling n-heptane. Refers to polypropylene. In this case, a propylene homopolymer may be used, or a copolymer of isotactic polypropylene having stereoregularity and another α-olefin may be used. The crystalline polypropylene may be a commercially available product, or may be manufactured and used. The method for producing crystalline polypropylene is not particularly limited, and can be appropriately selected from conventional methods for producing crystalline polypropylene and applied.

The α-olefin used for copolymerization with crystalline polypropylene includes α-olefins having 2 to 8 carbon atoms.
-Olefins such as ethylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1 and the like are preferred. Among these, ethylene or butene-1 is particularly preferable.

In the present invention, the crystalline polypropylene is preferably a propylene homopolymer, a random copolymer or block copolymer of propylene / ethylene containing an ethylene component of 30% by weight or less, preferably 1 to 25% by weight. And a random copolymer or block copolymer of propylene / butene-1 containing 20% by weight or less of butene-1. Among them, a copolymer of ethylene or butene-1 and propylene is particularly preferred from the viewpoint of applications such as a film and a sheet of the resin composition of the present invention. The crystalline polypropylene of the layer (a) can be used alone or in combination of two or more.

In the present invention, (a) for forming a layer,
The method for preparing the resin composition of the amorphous polyolefin and the crystalline polypropylene is not particularly limited, and is a method commonly used in a conventional method for producing a polypropylene composition, for example, a kneader, a Banbury mixer, a kneading machine such as a roll, Heat melting and kneading can be performed using a single screw or twin screw extruder or the like. Further, in the present invention, various additives and fillers such as a heat resistance stabilizer, an antioxidant, a light stabilizer, an antistatic agent, a lubricant, and the like may be added to the resin composition constituting the layer (a) as required. A nucleating agent, a soft burner, a pigment or a dye, calcium carbonate, calcium sulfate, barium sulfate, magnesium hydroxide and the like can be blended as required, and these can be crosslinked. In particular, when imparting soft flammability, 20 to 60 parts by weight of magnesium hydroxide or magnesium carbonate is added to the multilayer film.

In the present invention, the resin composition for the (a) layer comprises the above-mentioned amorphous polyolefin alone or two or more kinds thereof.
It is made of crystalline polypropylene, and can be obtained by blending an amorphous polyolefin in an amount of 10 to 70% by weight, preferably 15 to 60% by weight. If the amount of the amorphous polyolefin is less than 10% by weight, it is not different from crystalline polypropylene. When the amount of the amorphous polyolefin is more than 70% by weight, the film becomes too soft and the handling of the obtained film is poor.

In the present invention, the crystalline polypropylene resin for the (b) layer is preferably of the same grade as the crystalline polypropylene resin used for the (a) layer. With such a configuration, the adhesiveness between the layer (a) and the layer (b) can be further improved.

In the present invention, the multilayer film (A) comprises:
It is essential that the (a) layer and the (b) layer are alternately laminated, and that the outermost layer is the (b) layer. Therefore, at least a three-layer structure of (b) / (a) / (b) is required, and further, (b) / (a) /
(B) / (a) / (b) five-layer structure, (b) / (a) /
(B) / (a) / (b) / (a) / (b) seven-layer structure,
… And so on.

In the present invention, the layer (a) contributes to imparting flexibility to the whole film, and also contains a crystalline polypropylene, so that the heat resistance and stiffness of the film can be improved. However, the amorphous polyolefin used has a strong surface tackiness, especially when the molecular weight is low. On the other hand, since the layer (b) contributes to the strength and heat resistance of the film and has little surface tackiness, the layer (b) constitutes at least one outer layer as described above, and the layer (a) By constituting the inner layer side, at least one can be a flexible film without surface tackiness. Therefore, as described above, by appropriately changing the number of layers, the mechanical properties of the composite film can be adjusted, and the composite film can be adapted to various uses.

In the present invention, the thickness of each layer constituting the multilayer film (A) is not particularly limited, and can be arbitrarily selected according to the application. Usually, each layer is formed in a range of about 2 to 1000 μm. Further, the ratio of the thickness of the layer (a) to the thickness of the layer (b) is not particularly limited. Preferably, as described above, the layer (a) contributes to the flexibility of the film, and the layer (b) performs the function of preventing surface tackiness. (A) the total thickness of the layer is 20 times the thickness of the laminated film.
To 99%, more preferably 30 to 95%.

In the present invention, the production method of the laminated film is as follows:
It is not particularly limited. For example, a coextrusion lamination method, a lamination method, a dry lamination method, or the like can be used. Of these, the co-extrusion lamination method in which melt bonding is performed is preferred. Specifically, for example, melt extrusion using an extruder suitable for the number of laminations, after laminating in a molten state by a known method such as a T-die method or an inflation method, a cooling roll,
The multilayer film (A) can be produced using a method of cooling with water or air.

In the present invention, the multilayer film (A) comprises:
Surface treatment can be performed to improve printability, lamination, and adhesive applicability. Examples of the surface treatment method include a corona discharge treatment, a plasma treatment, a flame treatment, and an acid treatment. In the present invention, any of the methods can be used. A plasma treatment, a flame treatment, and a corona discharge treatment are preferable because continuous treatment is possible and can be easily performed before a winding step in a film manufacturing process, and among these, corona discharge treatment is preferred in terms of simplicity. Is most preferred. In addition, the present laminated film can be subjected to uniaxial or biaxial stretching, compressed air, vacuum forming, or the like. In the present invention, the multilayer film (A) is laminated as described above,
After being cooled and solidified, after the above-mentioned treatment as necessary, it is wound up and then subjected to the next step, for example, a secondary processing step such as printing, laminating, application of an adhesive, heat sealing, etc., and the intended use. Can be used for

Next, the polyalkylene terephthalate resin and the polyalkylene naphthalate resin for forming the film (B) used in the present invention will be described. Representative of these thermoplastic polyester resins include:
Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly 1,4-cyclohexyl dimethylene terephthalate (PCT), polyethylene 2,6-naphthalate (PEN), polybutylene-
2,6-naphthalate (PBN) and the like.

The polyester is not limited to a homopolymer, but may be a dicarboxylic acid and / or a constituent component of the polyester.
Alternatively, part of the diol may be replaced with another dicarboxylic acid and / or another diol. For example, polyalkylene terephthalate and polyalkylene naphthalate are composed of an aromatic dicarboxylic acid component (terephthalic acid or naphthalenedicarboxylic acid) and an alkylene glycol component (ethylene glycol, 1,4-butanediol, etc.). Examples of the component that can be substituted for part of the acid or phthalenedicarboxylic acid component include dicarboxylic acids or acid anhydrides thereof (for example, maleic acid, maleic anhydride, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Aliphatic dicarboxylic acids such as sebacic acid and dodecanoic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; phthalic acid, phthalic anhydride, isophthalic acid, diphenyl-4,4'-dicarboxylic acid, 3-sulfo acid Aromatic dicarboxylic acids such as isophthalic acid) It is shown. In polyalkylene terephthalate (PET or PBT), part of terephthalic acid is naphthalene-
It may be substituted with 2,6-dicarboxylic acid or the like, and in polyalkylene naphthalate, a part of naphthalenedicarboxylic acid may be substituted with terephthalic acid.
These dicarboxylic acids or acid anhydrides thereof can be used as a mixture of at least one kind or more.

Examples of diols that can partially replace alkylene glycol components (such as ethylene glycol and 1,4-butanediol) include, for example, ethylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, and polyethylene. Glycol, propylene glycol, dipropylene glycol,
Aliphatic diols such as tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,5-pentadiol, 1,6-hexanediol, and polytetramethylene glycol; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,
Alicyclic diols such as 2,2-bis (4-hydroxycyclohexyl) propane, and adducts of hydrogenated bisphenol A with alkylene oxides (such as ethylene oxide and propylene oxide); resorcinol, 2,2-bis ( 4-hydroxyphenyl) propane, an adduct of bisphenol A with an alkylene oxide (such as ethylene oxide or propylene oxide) (for example, 2,2′-bis (4-hydroxyethoxyphenyl) propane, 2,2′-bis ( 4-hydroxydiethoxyphenyl) propane, 2,2'-bis (4-
(Hydroxypolyethoxyphenyl) propane, 2,2 ′
-Bis (4-hydroxypropoxyphenyl) propane, 2,2'-bis (4-hydroxydipropoxyphenyl) propane, 2,2'-bis (4-hydroxypolypropoxyphenyl) propane, etc. Is exemplified. These diols can be used as a mixture of at least one kind.

Further, a part of terephthalic acid, naphthalene carboxylic acid component and alkylene glycol component may be substituted with hydroxycarboxylic acid. Examples of the hydroxycarboxylic acid include aliphatic hydroxycarboxylic acids such as glycolic acid and oxypropionic acid; and aromatic hydroxycarboxylic acids such as hydroxybenzoic acid. One or more of them can be used in combination.

The molecular weight of the above polyester resin is, for example, about 5,000 to 1,000,000, which is a weight average molecular weight.
0, preferably about 10,000 to 500,000, and often about 15,000 to 100,000. The intrinsic viscosity of polyester resin is 25 ± 1 ℃
When the solvent o-chlorophenol is used in at least about 0.5 dl / g or more, preferably 0.75 to 2.5 d
It is about 1 / g. The polyester for the film (B) may be used alone or as a blend of two or more.

The polyester resin film used as the film (B) may be either unstretched polyester or stretched polyester, but is preferably a stretched polyester film having excellent mechanical properties (for example, biaxially stretched polyethylene terephthalate film or polyethylene naphthalate film). Film and the like). When a polybutylene terephthalate film or a polybutylene naphthalate film having excellent heat resistance and mechanical properties is used, it is not always necessary to stretch.

Further, these polyester films can be laminated and used for the film (B).
The thickness of the polyester film for the film (B) is 2 to 2
00 μm, preferably 5-150 μm.

Next, the resin for forming the heat bonding layer on the polyester film (B) will be described. The resin forming the heat bonding layer is not particularly limited as long as it is a resin that can be heat bonded to the film (A) at a temperature equal to or lower than the melting point of the polyester resin for the film (B). For example, an amorphous polyolefin homopolymer or copolymer, a polymer blend thereof, or a graft or adduct of an unsaturated organic acid such as acrylic acid or maleic anhydride can be used. Among these, since the adhered surface on the side of the multilayer film (A) is crystalline polypropylene, the amorphous polyolefin having a propylene and / or butene-1 component content of 50% by weight or more, or unsaturated acid grafting or Adduct polyolefins are preferred. The method of forming the heat bonding layer is lamination,
Conventionally known methods such as coextrusion and coating can be used. The thickness of the heat bonding layer is 2 to 100 μm, preferably 5 to 50 μm. In the present specification, the “melting point or Tm” means a peak temperature measured at a heating rate of 10 ° C./min using differential scanning and calorimetry (DSC) in accordance with JIS K7121. I do.

The composite film of the present invention is a curable type, and a clear coat layer capable of easily removing contaminants can be provided on the outer surface of the film (B), that is, on the surface opposite to the side on which the thermal adhesive layer is provided. . In this case, the clear coat agent is applied to the film (B) before lamination with the multilayer film (A) to provide a coat layer, or
After laminating, apply to the outer surface of film (B),
A coat layer can be provided. With the coat layer thus set, the hardness of the outer surface of the film (B) is further increased, the abrasion resistance is improved, and the contaminant adheres due to the easy removal of the contaminant by the coat layer. It can be easily detached.

As a method of applying the clear coat agent, for example, a roll coating method, a reverse coating method, a knife coating method, a curtain flow coating method, a spray coating method, a dip coating method, a flow coating method, etc. 1 to 50 μm in thickness, preferably 2 to 50 μm
It is applied so as to have a range of 10 μm. The drying is usually heated at 130 ° C. for about 30 seconds, but is not particularly limited to this. As the hardening type clear type antifouling easily removable protective coating agent used in the present invention, melamine resin-based, fluororesin-based, polyurethane resin-based, polysiloxane resin-based paints and the like can be used. In particular, polysiloxane resin
The coating film composed of the acrylic-modified polysiloxane resin and the curing catalyst has a high hardness and is inert to ordinary contaminant deposits, and can be removed very easily. Can be granted. For example,
Bleaching of cleaning solvents such as alcohol and thinner, and dilute aqueous solutions such as sodium hypochlorite and sodium hydroxide,
Even if it is not affected by mold inhibitors and is contaminated with foods such as curries, sauces, coffee and office supplies such as crayons, water-based markers, and oil-based magic inks, simply wipe it off with a dry cloth. And can always maintain cleanliness.

The present invention will be described below in more detail with reference to Examples, but the technical scope of the present invention is not limited thereto.

[0033]

【Example】

I. Molding of Multilayer Film (A) (Part 1) Molding of Multilayer Film (A) -1 (a) 25% by weight of an amorphous polyolefin (a product of Hustle, trade name "Bestplast 608") for the layer
And an additive such as a coloring agent was mixed with a resin raw material consisting of 75% by weight of crystalline polypropylene (trade name “YK121” manufactured by Ube Industries, Ltd.) and mixed with a tumbler. On the other hand (b)
For the layer, the above crystalline polypropylene “YK121”
Similarly, additives were blended and mixed. Then, these are fed to a three-layer T-die multilayer film forming machine,
A colored multilayer film (A) -1 having a (b) / (a) / (b) type three-layer structure was formed at a temperature of ° C. The finished thickness of each layer was 60 μm for the (a) layer and 15 μm for the (b) layer. (Part 2) Molding of Multilayer Film (A) -2 (a) Except that the amorphous polyolefin resin for the layer was replaced with Vestplast 608 and Lextax 92035 (a product of Lexen) was used, all the multilayer films were used. A colored multilayer film (A) -2 having a (b) / (a) / (b) type three-layer structure was formed in the same manner as (A) -1.

II. Preparation of Film (B) (Part 1) Preparation of Film (B) -1 A 25 μm-thick polyethylene terephthalate film (a product of Teijin Limited, trade name “Tetron Film-SP”)
2 "... hereinafter referred to as PET-1)
Dry laminating a 0 μm film (product of Daicel Chemical Industries, Ltd., trade name “Zeneshi CPPC128”
PET-1 provided with the heat bonding layer (1) was produced. (Indicated as Film (B) -1.) As an adhesive for dry lamination in this processing, a resin solution (trade name: AD563, manufactured by Toyo Morton Co., Ltd.) was used, and the coating amount was about 5 g / m ^2. (Solid content). Next, the surface of the thermal adhesive layer (1) was subjected to corona treatment, and a marble pattern was gravure-printed using an amide-based ink (trade name “PANN Color” manufactured by Toyo Ink Mfg. Co., Ltd.). (Mitsubishi Chemical Corporation, product name "Modic P300")
F ”resin by a single-layer T-die film forming machine
PE formed with a heat bonding layer (2) in the same manner as in the film (B) -1 except that a film formed into a film having a thickness of 20 μm at 20 ° C. was replaced with Seneshi CPP C128.
T-1 was produced. (Indicated as Film (B) -2.) (Part 3) Production of Film (B) -3 Instead of PET-1, a 25 μm thick polybutylene terephthalate film (a product of Daicel Chemical Industries, Ltd.,
Film (B) except that Thermolite ES03 (trade name is hereinafter referred to as PBT-1) was used.
In the same manner as in -2, a PBT provided with the heat bonding layer (2) was produced. (Indicated as Film (B) -3.) (Part 4) Production of Film (B) -4 Corona treatment is applied to the surface of PBT-1 opposite to the surface on which the thermal adhesive layer is provided, and a curable clear coat agent is provided. (Kansai Paint Co., Ltd.
Apply the product and product name “CG Clear” and apply 30 ° C at 130 ° C.
After drying for 2 seconds, PBT-1 provided with a cured coating layer having a finish thickness of 5 μm, which was easily removable, was prepared. (Hereinafter, this film is referred to as PBT-2.) Then, in the same manner as in the film (B) -3 except that PBT-2 was used, PBT-2 provided with the heat bonding layer (2) was prepared. Produced.
(Displayed as Film (B) -4.)

III. Preparation of Composite Film The multilayer film (A) and the film (B) prepared as described above are superimposed in a combination shown in Table 1, sandwiched between a pair of embossed plates, and a silicone rubber sheet is used as a cushion material by a press machine. The lower plate was pressed at 60 ° C., the upper plate at 170 ° C., and the pressure at 10 kg / cm ² for 20 seconds, followed by heat lamination to produce composite films of Examples 1 to 5.

IV. Production of Control Sample (Comparative Example 1) A control composite film was produced in the same manner as in Example 1, except that no thermal adhesive layer was provided on PET-1. (Comparative Example 2) M used in producing Film (B) -2
A control film was prepared by heat laminating the dic P300FT die-formed film to the multilayer film (A) -2 in the same manner as in the example. Comparative Example 3 A dry laminated film of the multilayer film (A) -2 and PET-1 was produced. In this case, the dry laminating adhesive and the dry laminating processing conditions were the same as in the production of the film (B) -1. (Comparative Example 4) PVC film having a thickness of 120 μm (product of Riken Vinyl Co., Ltd., trade name “W-500”, hereinafter referred to as PV)
Indicated as C-1. ) And a 120 μm thick PVC film (product of Riken Vinyl Co., Ltd., trade name “BK-15”)
-Hereinafter, it is indicated as PVC-2. ) Was heat-laminated in the same manner as in the example to produce a PVC composite film.

V. Quality evaluation method and test result of test double film Test method 1) Adhesion between (A) / (B): Adhesion strength between multilayer film (A) and film (B) Of width 15mm,
The test was performed with a T-type stripper at a stripping speed of 300 mm / min. 2) Outer surface strength of film (B): Pencil hardness according to JIS
It was measured according to K5400. 3) Solvent resistance: The heat-resistant resin layer was rubbed with a gauze impregnated with toluene ten times by hand, and the surface of the heat-resistant resin layer was visually observed, and evaluated according to the following criteria. ：: No change in appearance △: Slight trace of rubbing remains X: Mark of rubbing remains remarkably (a: Surface is immersed in toluene, b: Gauze rubs and scratches) 4) Stain resistance: Heat resistance The conductive resin layer was marked with an oil-based OHP (overhead projector) marker (Plus Co., Marker PE-010M black), left for one day, wiped off strongly with gauze, and the degree of contamination was evaluated according to the following criteria. ◎: Magic is first repelled into a polka dot and can be cleaned neatly. で き る: Can be cleaned neatly. ：: Marks of markers remain thin. X: Markers cannot be removed. The results are shown in Table 1.

Table 1

Evaluation of Test Results of Control Example Comparative Example 1: The multilayer film (A) and the film (B) cannot be adhered. Comparative Example 2: Unsuitable as a decorative sheet because of low surface hardening and easy damage. Comparative Example 3: It is not practical because a separate step called dry lamination is required. Conventional equipment cannot be used effectively. Processing costs are high. Comparative Example 4: Inferior in solvent resistance and stain resistance, and cannot respond to recent environmental problems because it is a chlorine-containing material.

[0040]

As described above, the multilayer film of the present invention has a high hardness, excellent contamination resistance, a flexibility, Since it is composed of a strong multi-layered base material and, if necessary, it can be given an arbitrary pattern print on the inner layer surface,
In particular, it is useful as a surface material for decorative sheets.

Claims (6)

[Claims] 1. An amorphous polyolefin having a propylene and / or butene-1 component content of 50% by weight or more
70% by weight and 90-30% by weight of crystalline polypropylene
A film comprising a resin composition layer (a) composed of: and a layer (b) composed of crystalline polypropylene, wherein at least three layers are laminated, and both outer layers are composed of (b) layers. ) And a thermoplastic polyester film (B) having a thermal adhesive layer on at least one surface, and a film (B) and a multilayer film (A) laminated via the thermal adhesive layer of the film. 2. The composite film according to claim 1, wherein at least one of the bonding surfaces of the multilayer film (A) and the heat bonding layer of the film (B) is printed in advance. 3. The composite film according to claim 1, wherein the thermal adhesive layer of the film (B) is a polyolefin having a propylene and / or butene-1 component content of 50% by weight or more. 4. The composite film according to claim 1, wherein the thermoplastic polyester film of the film (B) is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), or polyethylene naphthalate (PEN). 5. The composite film according to claim 1, wherein the film (B) is a biaxially stretched film. 6. The composite film according to claim 1, wherein a cured type clear coat layer is provided on the outer surface of the film (B) to enhance the stain resistance of the surface.