JPH11286086A - Composite film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite film for a non-chlorine type decorative sheet which is excellent in designability, solvent resistance, stain resistance, secondary processability and economical efficiency. SOLUTION: In a composite film, a polyolefin film A and a thermoplastic polyester resin film B 200 deg.C or above in melting point which has a heat-adhesive layer at least on one side are laminated through the heat-adhesive layer of the polyester resin film B and an ink layer. The composite film has both merits of the polyolefin film A and of the polyester film B, is excellent in adhesion, solvent resistance, chemical resistance, designability including printability and embossing, scratch resistance, economical efficiency and environmental protection by its being non-chlorine type. By forming a curable clear coat layer, the composite film has good stain resistance and is useful as a surface decoration sheet material for surface protection materials, especially for building materials and furniture.

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, and more particularly to a composite film mainly composed of a thermoplastic polyester resin 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 material for furniture and the like, a vinyl chloride (PVC) sheet or a sheet provided with a coating layer on the surface of the PVC sheet or laminated with a film has been used. However, this P
The VC sheet is excellent in design and cost performance, but not only has insufficient properties such as solvent resistance, chemical resistance, and stain resistance, but also has a recent social demand for global environmental protection. The use of chlorine component resins tends to be avoided.

[0003] Therefore, it is non-chlorine, solvent resistant,
The use of economical biaxially stretched polyethylene terephthalate (hereinafter sometimes abbreviated as PET) films having excellent chemical resistance and printability has been studied. However, this PE
T film has insufficient adhesiveness, and when laminating several films to finish as a decorative sheet, it is necessary to apply an adhesive once off-line and then laminate by a method such as dry lamination. There was a problem.

[0004] Recently, economical olefin materials which are non-chlorine and have excellent solvent resistance, chemical resistance and stain resistance and are economical have been studied as PVC substitute materials.
As with ET films, not only does it have problems with laminating properties, but because it is a relatively soft material, the surface is easily scratched (poor in abrasion resistance). There were drawbacks such as being unsuitable for coating for processing.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a film for a decorative sheet having a novel structure which combines the characteristics of a thermoplastic polyester resin film with the advantages of a polyolefin film. The inventors of the present invention have conducted intensive studies, and as a result, using a polyolefin film as a base material, a thermoplastic polyester resin film having a large surface hardness as a surface material, and heating and laminating these with a heat bonding layer, This led to the development of a chlorine-free composite film for decorative sheets, which is excellent in water resistance, solvent resistance, stain resistance, secondary workability, and economy.

[0006]

According to the present invention, there is provided a polyolefin film (A) and a thermoplastic polyester resin film (B) having a thermal adhesive layer on at least one surface and having a melting point of 220 ° C. or more, comprising: Another object of the present invention is to provide a composite film characterized by being laminated with a heat bonding layer of a resin film (B) and an ink layer interposed therebetween.

The thickness of the composite film of the present invention, various films or layers constituting the film are not particularly limited, and the term “film” may be replaced with “sheet” in the range of commonly used terms. Even if it is substituted for, since the effect of the present invention is the same, "film" in the present specification
All of the terms also include "sheets".

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Polyolefin film (A) used in the present invention
Has a propylene and / or butene-1 component content of 50
% By weight or more of amorphous polyolefin 10 to 70% by weight
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). Or a single-layer film (A2) composed of only the layer (b).

In the present invention, the amorphous polyolefin used in the layer (a) (hereinafter referred to as “amorphous polyolefin”) is propylene and / or butene-polyolefin.
Any amorphous olefin polymer having a content of 1 of 50% by weight or more 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.

[0010] 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.

Among the above-mentioned amorphous polyolefins, 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 the case of the intended production, for example, it can be obtained by polymerizing the 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 the stability of the raw material supply and the stability of the quality, it is preferable to use a predetermined amorphous polyolefin produced for the purpose. In addition, if there is a corresponding suitable commercial product, a commercial 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 preferably 30% by weight or less, more preferably 1 to 20% by weight. 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, the copolymer mainly composed of propylene and the 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, (a) the resin composition for the 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 for the layer (b) may be the same as the crystalline polypropylene used for the layer (a), and may be of the same grade as the crystalline polypropylene used for the layer (a). Is desirable.
With such a configuration, the adhesiveness between the layer (a) and the layer (b) can be further improved.

In the present invention, the polyolefin film (A) may be a single-layer film (A2) having only the (b) layer, but when the polyolefin film (A) is a multilayer film (A1), the above-mentioned (a) layer and ( It is essential that the b) layers 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) are formed into a multilayer structure such as a seven-layer structure,...

In the present invention, the layer (a) contributes to imparting flexibility to the whole film, and can also exhibit heat resistance and stiffness of the film by containing crystalline polypropylene. 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 (A1) 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. (A)
The ratio of the thickness of the layer to 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 2 times the thickness of the laminated film.
It is configured to be 0 to 99%, more preferably 30 to 95%. In the case of a single-layer film (A2), the total thickness is 2
It is formed in a range of 1000 μm.

In the present invention, the method for producing the multilayer film (A1) 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 T-die method or inflation method, using a cooling roll, a method of cooling with water or air cooling. Thus, the multilayer film (A1) can be manufactured.

In the present invention, the multilayer film (A1)
Can be subjected to a surface treatment 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.

The polyolefin film (A) used in the present invention may be a colored concealing film using a coloring material and a concealing material. When a colored concealing film is used, the total light transmittance (measured in accordance with JIS K 7105) is 20%.
The following should be good. If the total light transmittance exceeds 20%, it is difficult to impart design properties. Any known coloring material or concealing material may be used depending on the purpose, and may be added by mixing or dispersing the polyolefin film (A) during molding.

The main resin other than the thermal adhesive layer of the thermoplastic polyester resin film (B) used in the present invention includes a polyalkylene terephthalate resin and a polyalkylene naphthalate resin having a melting point of 220 ° C. or higher. Representative examples of these thermoplastic polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate (hereinafter sometimes abbreviated as PBT),
Examples thereof include poly-1,4-cyclohexyldimethylene terephthalate (PCT), polyethylene-2,6-naphthalate (PEN), and polybutylene-2,6-naphthalate (PBN).

The thermoplastic polyester resin is not limited to a homopolymer, and a part of the dicarboxylic acid and / or diol which is a constituent component of the polyester may be replaced with another dicarboxylic acid and / or another diol. 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.). It can be replaced with a component.

The component which can be substituted for a part of the terephthalic acid or naphthalenedicarboxylic acid component includes dicarboxylic acid or an acid anhydride thereof (for example, maleic acid, maleic anhydride, succinic acid, adipic acid, pimelic acid, suberic acid) Aliphatic dicarboxylic acids such as azelaic acid, sebacic acid and dodecanoic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; phthalic acid, phthalic anhydride;
Aromatic dicarboxylic acids such as isophthalic acid, diphenyl-4,4'-dicarboxylic acid, and 3-sulfoisophthalic acid). In polyalkylene terephthalate (PET or PBT), part of terephthalic acid may be substituted by naphthalene-2,6-dicarboxylic acid or the like. In polyalkylene naphthalate, part of naphthalene dicarboxylic acid may be substituted by terephthalic acid May be substituted. These dicarboxylic acids or acid anhydrides thereof can be used as a mixture of at least one kind or more.

Examples of the diol which can partially replace the above-mentioned alkylene glycol component (ethylene glycol, 1,4-butanediol, etc.) include, for example, ethylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, 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; , 4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane, etc., and adducts of hydrogenated bisphenol A with alkylene oxides (eg, ethylene oxide and propylene oxide) Alicyclic diols; adducts of resorcinol, 2,2-bis (4-hydroxyphenyl) propane, bisphenol A and alkylene oxides (such as ethylene oxide and propylene oxide) (for example, 2,2'- Scan (4-hydroxyphenyl) propane, 2, 2 '- bis (4-hydroxy-diethoxy phenyl) propane,
2,2'-bis (4-hydroxypolyethoxyphenyl) propane, 2,2'-bis (4-hydroxypropoxyphenyl) propane, 2,2'-bis (4-hydroxydipropoxyphenyl) propane, 2,
2'-bis (4-hydroxypolypropoxyphenyl)
And aromatic diols such as propane. These diols can be used as a mixture of at least one kind.

Further, a part of terephthalic acid, naphthalenedicarboxylic 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 thermoplastic polyester resin is, for example, about 5,000 to 1,0
00,000, preferably 10,000 to 500,0
00, and often around 15,000 to 100,000. The inherent viscosity of the thermoplastic polyester resin is at least about 0.5 dl / g, preferably at least about 0.5 dl / g when the solvent o-chlorophenol is used at 25 ± 1 ° C.
It is about 75 to 2.5 dl / g. The polyester resin for the thermoplastic polyester resin film (B) may be used alone or as a blend of two or more.

Thermoplastic polyester resin film (B)
The polyester resin film used as a main material may be an unstretched polyester film or a stretched polyester film, but a stretched polyester film having excellent mechanical properties (for example, a biaxially stretched polyethylene terephthalate film or a polyethylene naphthalate film, etc.) ) Are preferred. In addition, heat resistance, polybutylene terephthalate film with excellent mechanical properties,
When using a polybutylene naphthalate film, it is not always necessary to stretch.

These polyester resin films can be laminated and used for the thermoplastic polyester resin film (B). When laminating, the constituent components of each polyester resin film may be the same or different. As a method of forming a laminate, an extrusion lamination method, a dry lamination method, coextrusion melting, an extrusion method, or the like is used.

Thermoplastic polyester resin film (B)
The thickness of the polyester resin film for use is preferably from 2 to 200 μm, and more preferably from 5 to 150 μm.

As the main material for forming the thermal adhesive layer of the thermoplastic polyester resin film (B) used in the present invention, the thermoplastic material constituting the thermoplastic polyester resin film (B) without impairing the function of the present invention. The material is not particularly limited as long as it is a material that can be thermally bonded at a temperature lower than the melting point of the polyester resin, but is preferably a polybutylene terephthalate-based polyester (P) having a melting point in the range of 150 to 215 ° C.
BT) resin is good. As such a PBT resin, terephthalic acid and a part of 1,4-butanediol which are components of a PBT homopolymer having a melting point of 225 ° C. have a melting point of 15%.
PBT-based copolymer resins substituted with other components in the range of 0 to 215 ° C. are exemplified.

The component capable of replacing a part of the terephthalic acid component is dicarboxylic acid or an acid anhydride thereof, such as maleic acid, maleic anhydride, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, or the like. 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, naphthalene-2,
Examples thereof include aromatic dicarboxylic acids such as 6-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, and 3-sulfoisophthalic acid. These dicarboxylic acids or acid anhydrides thereof can be used as a mixture of at least one kind.

On the other hand, examples of the glycol which can be substituted for a part of the 1,4-butanediol component include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and polypropylene glycol. Aliphatic diols such as triethylene glycol, 1,3-butylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, and polymethylene glycol;
1,4-cyclohexylglycol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane, etc., and water-vaporized bisphenol A
And an alicyclic diol such as an adduct of an alkylene oxide such as ethylene oxide or 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)
Aromatic diols such as propane, 2,2′-bis (4-hydroxydipropoxyphenyl) propane, and 2,2′-bis (4-hydroxypolypropoxyphenyl) propane are exemplified. These dihydric alcohols can be used as a mixture of at least one kind. As the diol component, those described above can be used, but the use of 1,4-butanediol is preferred from the viewpoints of crystallization during film formation and maintaining heat resistance. The ratio (mol) in the diol component is 1,
4-butanediol / other components = 80 / 20-100 / 0
%, Preferably 1,4-butanediol / other component = 1
It is preferable to adjust the melting point on the dicarboxylic acid side to 00/0% to obtain a resin having preferable physical properties.

The number and amount of other components to be copolymerized with the PBT copolymer resin are not particularly limited, and the melting point is 150 to 215.
The temperature may be within the range of ° C. 215 ° C melting point
If the melting point is less than 150 ° C., the crystallinity, crystallization speed, heat resistance, and mechanical properties of the PBT-based copolymer resin are deteriorated. This causes a problem that the film properties are reduced and the film causes blocking.

Thermoplastic polyester resin film (B)
The molecular weight of the PBT resin forming the heat bonding layer of the above can be in a conventionally known range. For example, the weight average molecular weight of the resin is usually about 5,000 to 1,000,000
00, preferably about 10,000 to 500,000. The intrinsic viscosity is at least about 0.5 dl / g or more, preferably about 0.75 to 2.5 dl / g when chlorophenol is used as a solvent at a temperature of 25 ± 1 ° C.

Thermoplastic polyester resin film (B)
The polybutylene terephthalate-based polyester resin forming the heat-bonding layer of the above-mentioned polyester resin has a range of not impairing its physical properties for the purpose of improving durability such as water resistance and chemical resistance, that is, 5 to 5 parts with respect to the polybutylene terephthalate-based polyester resin.
You may mix | blend a polycarbonate resin in the range of 0 weight%. The compounding amount is preferably 10 to 40% by weight, more preferably 15 to 30% by weight. If the amount is too small, there is almost no effect of the compounding, and if the amount is too large, there is a problem that the thermal adhesion is reduced.

The thermoplastic polyester resin film (B) used in the present invention is formed by laminating a thermal adhesive layer such as a PBT resin layer on the main thermoplastic polyester resin film. As the lamination molding method, a conventionally known method, for example, a coextrusion method, an extrusion lamination method, a dry lamination method, or the like can be used.

In particular, if the thermoplastic polyester resin as the main material is P
In the case of an ET-based resin, an extrusion laminating method and a dry laminating method are preferably used for a layer formed by a lamination method. When the thermoplastic polyester resin as the main material is a PBT-based resin, coextrusion melting and extrusion of a T-die or incolation are preferably used since no stretching is required.

The laminated film may be used in an unstretched state, or may be uniaxially or biaxially, preferably biaxially stretched, if necessary.

As the stretching method, for example, a known stretching method such as a roll stretching, a rolling stretching, a belt stretching, a tenter stretching, a tube stretching, or a stretching method combining these can be applied. Stretching can be selected as appropriate, either uniaxially or biaxially.
The stretching ratio, stretching temperature, etc. can also be set according to the purpose.

More specifically, the thermoplastic polyester resin film (B) is preferably a biaxially stretched film having excellent mechanical properties when the main thermoplastic polyester resin is a PET resin. In the case of a PBT-based resin, sufficient physical properties can be obtained without stretching, so that it is not necessary to stretch the film economically.

Next, the method for laminating the composite film of the present invention will be described. The composite film of the present invention is a polyolefin film (A) [hereinafter sometimes abbreviated as film (A). ] And thermoplastic polyester resin film (B)
[Hereinafter, it may be abbreviated as film (B). Are laminated via the thermal bonding layer of the film (B) and the ink layer. The film (A), the film (B), and the ink layer can be laminated by a conventionally known method.
Lamination by thermal bonding is preferred.

As a method of thermal bonding, a conventionally known method such as a method of heating and pressing between hot press plates and a method of passing between hot rolls can be used. Typical processing temperatures for such devices are below 220-230 degrees,
The heat resistance of the main material of the film (B) must be higher than this, and the melting point of the heat bonding layer must be lower than 220 ° C. When the composite film of the present invention is formed by lamination by thermal bonding, it is preferable to perform thermal bonding at a temperature lower than the melting point of the main material of the film (B).

By adopting such a configuration, for example, at the time of embossing generally performed in this field,
The film (A) and the film (B) through the thermal adhesive layer and the ink layer of the film (B) can be simultaneously embossed and laminated, which is a great practical advantage.

In the present invention, the ink layer is previously continuous or discontinuous on at least one of the bonding surfaces of the polyolefin film (A) and / or the thermoplastic polyester resin film (B) with the ink layer of the thermal adhesive layer. Formed.

Examples of the material for forming the ink layer include an ink obtained by kneading a metal powder, an inorganic pigment, an organic pigment or the like into a vinyl, acrylic, polyester or urethane vehicle. The ink layer is formed by using the ink as described above, and forming a heat-adhesive layer of the film (A) or / and the film (B) in the form of a grain, a stone, a grain, an abstract pattern or on the entire surface (so-called solid printing). It is formed on the joining surface side by curing after printing (generally gravure printing).

In the present invention, the adhesive strength between the thermal adhesive layer of the film (A) and the thermal adhesive layer of the film (B) via the ink layer is a T-shaped peel strength (measured according to JIS K 6854) of 400 g / 15 mm. The width is preferably not less than the width, more preferably not less than 800 g / 15 mm, more preferably not less than 1500 g / 15 mm. This characteristic is realized by the structure of the film (B) and the ink layer described above.

According to the present invention, the film (A) and the film (B) can be bonded only by a thermal bonding process generally performed in the field, which has a great advantage in practical use.

In the composite film of the present invention, the curable clear coat layer can be formed on the outer surface of the film (B), that is, on the surface opposite to the surface on which the heat bonding layer is formed. In this case, a curable clear coat layer is previously formed on the film (B) before bonding to the film (A), or a curable clear coat layer is formed on the outer surface of the film (B) after bonding. Can be formed. The curable clear coat layer provided in this manner further increases the hardness of the outer surface of the film (B), improves the scratch resistance, and allows the contaminants to adhere to the coating layer due to the easy removal of the contaminants. Can be easily detached.

As a method of forming a curable clear coat layer, a clear coat agent is used, for example, a roll coating method, a reverse coating method, a knife coating method, a curtain flow coating method, a spray coating method,
Dried coating method, flow coating method, etc., dry film thickness 1-5
The coating is performed so as to have a thickness of 0 μm, preferably 2 to 10 μm. The drying is usually heated at 130 ° C. for about 30 seconds, but is not particularly limited to this. In the present invention, as a material for forming the curable clear coat layer,
Melamine resin, fluorine resin, polyurethane resin,
A coating agent mainly composed of a polysiloxane resin or a modified resin thereof can be used. In particular, a coating film composed of a polysiloxane resin, an acryl-modified polysiloxane resin, and a curing catalyst has a high hardness and is inert to ordinary contaminant deposits, and can be removed very easily. A stain-resistant surface can be provided. For example, alcohol, bleaching solvents such as thinners, sodium hypochlorite, dilute aqueous solutions such as sodium hydroxide, etc., are not affected by mold inhibitors, foods such as curry, sauce, coffee, etc. Even if it is stained with office supplies such as crayon, water-based marker, oil-based magic ink, etc., it can be easily wiped off with a dry cloth and the like, and can always be kept clean.

The composite film of the present invention can be subjected to surface treatment, blending of additives, etc. according to the purpose within a range not to impair the action of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Test Examples and Examples, but the technical scope of the present invention is not limited to these. Test Examples (1) Test Method 1) Adhesion For the composite films of Examples 1 to 3 and Comparative Examples 1 and 2,
Specimens with a width of 15 mm were prepared, and JIS K68
According to 54, the thermal adhesive layer of the film (B) and the film (A) are peeled in a T-shape at a peeling speed of 300 mm / min, and the load (kg) at the time of peeling is measured.

2) Embossability The composite films of Examples 1 to 3 and Comparative Example 2 were embossed, and then sandwiched between an upper transparent plate (180 ° C.) and a lower transparent plate (60 ° C.) at 30 kgf / kg. The film (B) is visually evaluated based on a criterion by pressure bonding with a pressure of ² cm ² . Judgment criteria ○: Same as PVC decorative sheet △: Slightly inferior to PVC decorative sheet ×: Emboss pattern is thin

3) Pencil hardness The composite films of Examples 1 to 3 and Comparative Example 2 were placed on a glass plate, and the surface on the film (B) side was rubbed with a pencil having a different hardness, and the presence or absence of scratches was visually checked. I do.

4) Antifouling Property Black oil-based magic was applied to the surface of the composite film of Examples 1 to 3 and Comparative Example 2 on the film (B) side, and then wiped off with a rag to visually observe the surface. Evaluate based on criteria. Criteria ○: Wipe off without trace. △: Slight trace remains ×: Cannot be wiped

(2) Test Results The results of Test Examples 1) to 4) are shown in Table 1.

[Table 1]

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Example 1 (1) Production of Film (A) (a) 25% by weight of an amorphous polyolefin (trade name "Bestplast 608", manufactured by Hustle Co.)
Crystalline polypropylene (trade name "Y" manufactured by Ube Industries, Ltd.)
K121 ") An additive such as a coloring agent was blended with a resin raw material consisting of 75% by weight, and mixed with a tumbler. On the other hand, for the layer (b), an additive was similarly blended and mixed with the crystalline polypropylene “YK121”. Next, these were fed to a three-layer T-die multilayer film forming machine, and a colored multilayer film (A1) having a (b) / (a) / (b) type three-layer structure was formed at 230 ° C. The finished thickness of each layer is
The (a) layer was 60 μm, and the (b) layer was 15 μm. (2) Production of film (B) A PBT resin film having a thickness of 15 μm (manufactured by Polyplastics Co., Ltd., trade name: 600FP, hereinafter PBT)
Two resin layers. ) And has a melting point of 170
Polycarbonate (hereinafter sometimes abbreviated as PC) is added to PBT copolymer resin at 85 ° C by weight ratio of 85/15 (PBT / P
C) The PBT (PBT1) resin blended to become C) is laminated by co-extrusion using a co-extrusion machine (multi-manifold die), and a 10 μm-thick heat bonding layer (PB) is formed.
T1 resin layer) and a film having a thickness of 25 μm. (3) Production of composite film Using acrylic ink on one side of film (A),
An ink layer was formed. Thereafter, the film (A) and the film (B) are overlaid via the ink layer of the film (A) and the heat bonding layer (PBT1 resin layer) of the film (B), and the temperature is 180 ° C. for 20 seconds by a hydraulic press. , Pressure 1
The composite film was adhered and laminated under an adhesion condition of 0 kg / cm ² to obtain a composite film.

Example 2 (1) Production of Film (A) Film (A) was produced in the same manner as in Example 1. (2) Production of Film (B) An easy-adhesion PET resin film (P72, manufactured by Toray Industries, Inc., trade name: P72) having a thickness of 15 μm was used as a main material, and a PBT1 resin layer similar to that of Example 1 was used as a thermal adhesive layer. Using an extruder, extrusion laminating is performed, and a 10 μm-thick heat bonding layer (PB
T1 resin layer) and a film having a thickness of 25 μm. (2) Production of Composite Film An ink layer was formed on one surface of the film (A) using a polyester-based ink. Thereafter, the film (A) and the film (B) are laminated via the ink layer of the film (A) and the heat bonding layer (PBT1 resin layer) of the film (B), and laminated as in Example 1 to form a composite film. I got

Example 3 A gravure coat was used on the easy-adhesion PET surface of the same composite film as in Example 2 except that the ink layer was formed using a urethane-based ink, and a curable clear coat for preventing contamination was used. An agent (manufactured by Kansai Paint Co., Ltd., trade name: CG Clear) is applied to a dry thickness of 2 μm and dried.
A composite film having a thickness of 27 μm was obtained.

Comparative Example 1 A composite film produced in the same manner as in Example 2 except that the composite film had no ink layer was used as Comparative Example 1.

Comparative Example 2 (3) Production of Composite Film A film (A) similar to that of Example 1 and a film (B) similar to that of Example 2 were combined with a heat bonding layer (PBT1) of film (B).
And a dry lamination using a dry laminating agent to obtain a composite film.

[0066]

Since the composite film of the present invention has the above-described structure, it has the properties of a thermoplastic polyester resin film and the advantages of a polyolefin resin film, and has adhesiveness, solvent resistance, chemical resistance, and printability. -It has excellent design properties such as embossability, scratch resistance, and economy, and is non-chlorine and has excellent environmental preservation. Further, by providing a hardening type clear coat layer, it is further excellent in stain resistance and is useful as a surface protective material, particularly a surface decorative sheet material used for building materials and furniture.

Claims (9)

[Claims] 1. A thermal bonding of a thermoplastic polyester resin film (B) with a polyolefin film (A) and a thermoplastic polyester resin film (B) having a thermal adhesive layer on at least one surface and having a melting point of 220 ° C. or more. A composite film characterized by being laminated via a layer and an ink layer. 2. The polyolefin film (A) has a propylene and / or butene-1 component content of 50%.
At least 10% by weight of amorphous polyolefin
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). 2. The composite film according to claim 1, wherein the film is a multilayer film composed of: or a single layer film composed of only the layer (b). 3. A thermoplastic polyester resin film (B)
3. The composite film according to claim 1, wherein the heat bonding layer comprises a polybutylene terephthalate-based polyester (PBT) resin having a melting point in the range of 150 to 215 ° C. 4. 4. A thermoplastic polyester resin film (B)
4. The composite film according to claim 3, wherein the polybutylene terephthalate-based polyester resin forming the thermal adhesive layer contains 5 to 50% by weight of polycarbonate. 5. A continuous or discontinuous ink layer is previously formed on at least one of the bonding surfaces of the polyolefin film (A) and / or the thermoplastic polyester resin film (B) with the ink layer of the thermal adhesive layer. The composite film according to any one of claims 1 to 4, wherein: 6. The polyolefin film (A) is a colored concealing film, and has a total light transmittance (JIS K 710).
The composite film according to any one of claims 1 to 5, wherein the composite film (measured based on No. 5) is 20% or less. 7. The adhesive strength between the polyolefin film (A) and the thermal adhesive layer of the thermoplastic polyester resin film (B) via the ink layer is 400 g / 15 mm width or more (JI
The composite film according to any one of claims 1 to 6, wherein the composite film is measured according to SK 6854). 8. A thermoplastic polyester resin film (B)
8. The stain resistance of the surface is enhanced by laminating a curable clear coat layer on the surface opposite to the surface bonded to the polyolefin film (A).
The composite film according to any one of the above. 9. The method according to claim 1, wherein the polyolefin film (A) and the heat-bonding layer of the thermoplastic polyester resin film (B) are heat-bonded at a temperature lower than 220 ° C. via an ink layer. A method for producing a composite film according to any one of the preceding claims.