JP2006205527A - Heat-adhesive laminated film for substrate skin and wall finishing material using the film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated film for the skin of a wall finishing material which has enough adhesive properties, is excellent in resistance to bending whitening, antifouling properties, scratch resistance (abrasion resistance), designability, embossment properties, etc. , and can be heat-adhered to a substrate such as a polyvinyl chloride substrate, a non-polyvinyl chloride substrate, or a polyolefin wall finishing substrate in particular without using an organic solvent type adhesive and a wall finishing material such as wallpaper or a decorative sheet obtained by laminating the laminated film on the polyolefin resin substrate or the polyvinyl chloride resin substrate. <P>SOLUTION: The heat-adhesive laminated film for the substrate skin is obtained by laminating the substrate and an adhesion resin layer on one side of a skin layer formed from an ionomer in which an ethylene-unsaturated carboxylic acid copolymer or a copolymer prepared by using ethylene and an unsaturated carboxylic acid as main components and the composition of them. The wall finishing material such as the wallpaper or the decorative sheet is obtained by laminating the laminated film on the polyolefin resin substrate or the polyvinyl chloride resin substrate. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a heat-adhesive laminated film for a base material skin and a wall covering material using the same, and in particular, a specific ionomer or a composition thereof is used as a skin layer, and the base sheet has good thermal adhesiveness on the back side of the layer. Due to the specific structure in which the adhesive resin layers shown are laminated, it is possible to adhere firmly to the base material sheet of wall coverings such as wallpaper and decorative sheets without causing solvent volatilization, but the surface has scratch resistance (wear resistance) ), A laminated film for a heat-adhesive substrate skin having excellent antifouling properties, design properties, embossability, and the like, and a wall covering material using the same.

  Conventionally, as a base material for wall covering materials such as wallpaper and decorative sheet, a soft polyvinyl chloride resin base material in which a plasticizer is blended has been widely used because it has various physical properties, is excellent in moldability and is inexpensive.

Soft polyvinyl chloride resin itself is rich in processability and can be finished with a very beautiful surface pattern and appearance as it is, but for applications that are highly demanding for decorativeness and aesthetics in interior decoration etc. The wall paper etc. which laminated | stacked the foaming polyvinyl chloride layer etc. on the surface layer are used.
However, in most cases, these soft polyvinyl chlorides contain a large amount of plasticizer of 40 parts or more with respect to 100 parts of the polyvinyl chloride resin. Therefore, in particular, in the case of expanded polyvinyl chloride, since the expansion ratio is about 2 to 6 times, the surface becomes porous, so that the surface is particularly susceptible to contamination.
As a solution to this problem, a method of covering the surface of the polyvinyl chloride resin with an antifouling film such as an acrylic resin film has been performed.
In addition, in order to obtain a special surface pattern that is difficult to implement on the surface of a polyvinyl chloride resin, such as a special textured satin pattern or a silky soft feel cloudy surface pattern, Conventionally, the surface of a vinyl base material has been often coated.

Polyvinyl chloride has many problems in terms of environmental measures such as generation of toxic gas such as hydrogen chloride gas and dioxin which is a carcinogenic substance at the time of incineration.
Therefore, recently, wall covering materials using non-polyvinyl chloride resins such as acrylic resins, ethylene / vinyl acetate resins, polyolefin resins, etc. as a base material as a substitute for polyvinyl chloride resins have rapidly spread. It's getting on.

These non-polyvinyl chloride-based wall coverings not only have the above-mentioned problems, but also contain a large amount of a plasticizer such as a soft polyvinyl chloride resin. Since it is difficult to bleed on the surface, there are advantages such as less surface contamination due to this, less environmental contamination, and less contamination due to attachment of suspended matters in the air.
In particular, polyolefin resin base materials such as polyethylene, polypropylene, and ethylene / α-olefin copolymers have good chemical stability, are harmless, and are inexpensive. Therefore, attempts to use them as base materials are frequently made.

However, the non-polyvinyl chloride resin as described above has a problem that once the dirt adheres, it is difficult to remove the contaminants.
Then, laminating | stacking the antifouling film as a skin resin layer on the surface similarly to having used with the polyvinyl chloride-type resin base material was examined.
As such antifouling films, ethylene / vinyl acetate copolymer saponified products (EVOH), acrylic films, etc. have been used, but the wall coverings laminated with these conventional films have been applied with paste. In the process of folding and stacking (training process), creases are generated, and since the crease is poorly restored after construction, the creases do not disappear and the aesthetics are remarkably impaired.
The film and the non-polyvinyl chloride resin substrate are generally laminated by a dry lamination method or the like.
At that time, since an organic solvent is used, the impact on the natural environment, the risk of fire, and the impact on the health of workers is a problem. Therefore, a film that can be laminated by thermocompression bonding without using an organic solvent. There was a strong demand.
Several proposals for solving the above problems have already been submitted. For example, Patent Document 1 discloses an adhesive resin layer made of an ethylene copolymer having a melting point of 70 to 105 ° C., such as crystalline polypropylene. A wall covering which is laminated on an unstretched layer of an antifouling thermoplastic resin having a melting point higher than that of the adhesive resin so that a modulus value at 20% elongation of the laminated film is 0.5 to 7.0 N / 10 mm. An invention of an unstretched laminated film for protecting a material surface is disclosed.

Japanese Patent Laid-Open No. 2002-1883

  The laminated film of Patent Document 1 is excellent in thermal adhesiveness with non-polyvinyl chloride resin base materials such as polyolefin, hardly generates creases, and has good resilience of creases once generated. The polypropylene skin layer does not necessarily have sufficient scratch resistance and abrasion resistance, and has a number of defects such as innumerable fine scratches on the surface during a long period of use, which impairs the appearance.

  In addition, in order to avoid this drawback, when a polyethylene terephthalate resin (PET) skin layer is used instead of a polypropylene skin layer, the scratch resistance and abrasion resistance are improved, but bending whitening resistance, polyolefin base material, etc. This causes a new problem that the adhesiveness is not always sufficient.

  In particular, since the polyolefin resin substrate does not have a polar group in its skeleton, it may be difficult to select an adhesive resin to be used for thermal bonding with the skin resin layer, as far as the present inventors know, A heat-adhesive skin film for a polyolefin wallpaper base material in which all of the above problems have been solved has not yet appeared.

Therefore, the object of the present invention is to provide a non-polyvinyl chloride resin-based wall covering base material, particularly a polyolefin-based resin base material, with sufficient adhesive strength and resistance to bending whitening, as well as antifouling and anti-resistance properties. A laminated film for the skin of wall coverings that has excellent scratch resistance (abrasion resistance), surface appearance, design, and embossability, and that can be thermally bonded to a substrate without using an adhesive containing an organic solvent. In offer.
Furthermore, another object of the present invention is to provide a laminated film for skin that is remarkably excellent in chemical resistance in addition to the above properties.
Another object of the present invention is to provide a laminated film for skin that exhibits the above-described effects even when applied to a polyvinyl chloride resin substrate, as in the case of a polyolefin resin substrate.
Still another object of the present invention is to provide wall covering materials such as wallpaper and decorative sheet, which are obtained by laminating the above laminated film for skin on a polyolefin resin substrate or a polyvinyl chloride resin substrate.

  According to the present invention, an ionomer based on an ethylenically unsaturated carboxylic acid copolymer or a multi-component copolymer containing ethylene and an unsaturated carboxylic acid as main constituent components, or an ionomer containing the ionomer as a main compounding component. There is provided a heat-adhesive laminated film for a base material skin, which is formed by laminating an adhesive resin layer having good thermal adhesiveness with a base material on one surface of a skin layer made of the composition.

The laminated film for a substrate skin of the present invention has a specific ionomer or a composition thereof as a skin layer. For example, in the case of a polyolefin-based substrate, ethylene / unsaturated carboxylic acid / (meth) acrylic acid ester copolymer Adhesive resin layer with excellent thermal adhesion to the base material such as coalescence resin, or in the case of polyvinyl chloride base material such as ethylene, carbon monoxide, (meth) acrylic acid alkyl ester copolymer resin The point of lamination by a method such as coextrusion is a prominent feature in construction.
As a result, the laminated film for skin of the present invention has excellent scratch resistance, abrasion resistance, antifouling property and the like as a skin layer when laminated on a wall covering base material made of polyolefin resin or polyvinyl chloride resin. Realizes excellent design appearance and embossability.
Among the above laminated films, those in which the resin material of the skin layer is a composition comprising the above ionomer, olefin / glycidyl monomer copolymer and polyolefin are further excellent in heat resistance and chemical resistance.

  The laminated film of the present invention can be particularly suitably used as a surface coating film for a wall covering base material such as wallpaper or a decorative sheet.

Moreover, it is preferable that the said laminated | multilayer film is that the adhesive resin layer has the adhesive strength (T peel) of 29 N / 25mm or more with respect to the base material which should be heat-bonded.
In particular, when the base material to be thermally bonded is a polyolefin resin sheet, the adhesive resin layer comprises an ethylene / unsaturated carboxylic acid / (meth) acrylic acid alkyl ester copolymer resin, an unsaturated carboxylic acid. Or an olefin polymer resin modified with an acid thereof, an ethylene / (meth) acrylic acid alkyl ester copolymer resin and an ethylene / vinyl acetate copolymer resin, or a resin layer comprising the above, or A resin layer comprising a blend composition of at least one kind of resin and a resin other than those described above, which further improves the workability and thermal adhesiveness of the adhesive resin layer, In the case of a vinyl chloride resin sheet, the adhesive resin layer is an ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer resin. Or a resin layer composed of a blend composition of the resin and other resin that further improves the workability and thermal adhesiveness of the adhesive resin layer, and realizes the above characteristics and particularly the base resin. From the viewpoint of thermal adhesive strength.

  Further, an embodiment in which the adhesive resin layer is composed of a plurality of layers having different resin types is preferable from the viewpoint of buffering the difference in physical properties between the skin layer and the substrate and further improving the adhesion between them.

  Moreover, according to this invention, the wall covering material formed by heat-bonding the laminated film of the said invention to the resin base-material surface is provided.

  In this case, when the resin base material is a soft polyvinyl chloride resin sheet, the adhesive resin layer of the laminated film is made of an ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer resin. It is preferable from the viewpoint of the above-described effects that the layer is a layer, particularly the adhesive strength with the base resin.

  When the resin substrate is a polyolefin resin sheet, the adhesive resin layer is acid-modified with an ethylene / unsaturated carboxylic acid / (meth) acrylic acid alkyl ester copolymer resin, an unsaturated carboxylic acid or a derivative thereof. From the same viewpoint as described above, the resin layer is composed of at least one selected from olefin polymer resins, ethylene / (meth) acrylic acid alkyl ester copolymer resins, and ethylene / vinyl acetate copolymer resins. preferable.

The laminated film for base material skin of the heat-adhesive material of the present invention has a specific ionomer or a composition thereof as a skin layer, and a specific adhesive resin layer exhibiting excellent heat adhesiveness to the base material by coextrusion or the like on the back side. The laminated structure does not cause inconvenience such as whitening due to bending, but also wall covering materials such as wallpaper and decorative sheet obtained by thermally bonding it to a polyvinyl chloride resin base or a polyolefin base. Has a strong thermal bond strength with the base resin, and is remarkably excellent in antifouling properties, scratch resistance (wear resistance), surface appearance, design properties, and embossability.
In particular, when the skin layer is made of the ionomer composition, the chemical resistance is remarkably excellent.

  Hereinafter, embodiments of the heat-adhesive laminated film for base material skin and the wall covering material using the same according to the present invention will be described in detail and specifically.

  The laminated film for substrate skin of the present invention is an adhesive resin layer that is laminated on one surface of an ionomer or a composition thereof and one surface of the skin layer, and has excellent thermal adhesion to a substrate resin such as a wallpaper substrate. As the ionomer base resin constituting the skin layer, in addition to the ethylene unsaturated carboxylic acid binary copolymer, ethylene and an unsaturated carboxylic acid unit are used as the main structural unit components, A multi-component copolymer obtained by copolymerizing these monomers can be used.

  The unsaturated carboxylic acid content in this ethylene / unsaturated carboxylic acid copolymer (including multi-components) is preferably in the range of 5 to 30% by weight, particularly 8 to 25% by weight. In the case of a polymer, the content of other monomer components is 40% by weight or less, preferably 30% by weight or less.

Examples of the unsaturated carboxylic acid constituting the copolymer include acrylic acid, methacrylic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, and the like, particularly acrylic acid or methacrylic acid. preferable.
Other monomers in the multi-component copolymer include vinyl esters such as vinyl acetate and vinyl propionate, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, and acrylic acid n- Unsaturated carboxylic acid esters such as butyl, isooctyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, dimethyl maleate, diethyl maleate, Examples thereof include carbon monoxide.

Moreover, as an ion source which ionizes the said base resin, zinc other than alkaline metals, such as alkali metals, such as lithium, sodium, and potassium, magnesium, and calcium, can be mentioned as a suitable example.
Particularly preferred ionomers are divalent metal ionomers, especially zinc or magnesium ionomers.
As the ionomer, a neutralization degree of 90% or less, particularly about 10 to 85% is preferable.

  The ionomer of the above-mentioned ethylene / unsaturated carboxylic acid copolymer is also melt flow rate (MFR) at 190 ° C. and 2160 g load from the viewpoint of processability and mechanical strength (according to JIS K7210-1999). Is preferably about 0.01 to 500 g / 10 min, particularly about 0.1 to 300 g / 10 min.

An ethylene / unsaturated carboxylic acid copolymer which is an ionomer base resin can be produced by radical copolymerization under high temperature and high pressure.
The ionomer can be obtained by reacting an ethylene / unsaturated carboxylic acid copolymer with a metal oxide, hydroxide, carbonate or the like.

  In the laminated film skin layer of the present invention, the above-mentioned ionomer can be used alone, but the composition of the ionomer and other resin, preferably a homopolymer of olefin, a copolymer of olefins, and an olefin and a polar monomer. For example, an olefin polymer selected from a copolymer of the polymer can be used as a composition mixed with an ionomer in an amount of equal to or less than equal weight, preferably equal to or less than 40% by weight, and particularly preferably equal to or less than 30% by weight.

  Examples of such olefin copolymers include ethylene homopolymers and copolymers of ethylene and α-olefins having 3 or more carbon atoms, which are generally medium / high density polyethylene, high pressure method low density polyethylene, Polyethylene known as chain low density polyethylene, linear ultra low density polyethylene, etc .; polypropylene known as propylene homopolymer, random copolymer or block copolymer of propylene and other α-olefins; poly Polyolefins such as -1-butene and poly-4-methyl-1-pentene, olefins and polar monomers, for example, vinyl esters such as vinyl acetate and vinyl propionate, methyl acrylate, ethyl acrylate, isobutyl acrylate , N-butyl acrylate, 2-ethylhexyl acrylate, acrylic The above ionomers such as unsaturated carboxylic acid esters such as glycidyl acid, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, glycidyl methacrylate, monomethyl maleate, monoethyl maleate, dimethyl maleate and diethyl maleate; carbon monoxide; Copolymers other than these can be mentioned.

When the olefin polymer is an ethylene / polar monomer copolymer, the polar monomer content is 30% by weight in consideration of wear resistance and scratch resistance, although depending on the blending amount. In the following, it is particularly preferable to use 20% by weight or less.
When the olefin polymer is polyethylene or ethylene / polar monomer copolymer, the melt flow rate (MFR) at 190 ° C. under a load of 2160 g (according to JIS K7210-1999) is 0. It is preferable to use 1-100 g / 10 min, particularly 0.2-50 g / 10 min. In the case of polypropylene, the melt flow rate (MFR) at 230 ° C. and 2160 g load is 0.1. It is preferable to use one having 1 to 100 g / 10 minutes, particularly 0.2 to 50 g / 10 minutes.

Preferable examples of the ionomer composition for the skin layer resin of the present invention include a composition comprising an ionomer, an olefin / glycidyl monomer copolymer and a polyolefin, and this ionomer composition layer is an ionomer as a resin component of the layer. Scratch resistance and wear resistance are almost inferior compared to when used alone, and realizes chemical resistance, surface hardness, heat resistance, designability (especially silky soft cloudy surface feel, etc.) And the appearance is superior).
In particular, when the total amount of ionomer, olefin / glycidyl monomer copolymer, and polyolefin is 100 parts by weight, the ionomer is 50 to 96.7 parts by weight, preferably 73 to 95.5 parts by weight, and more preferably 81 parts. ~ 94 parts by weight, olefin / glycidyl monomer copolymer is 0.3 to 10 parts by weight, preferably 0.5 to 7 parts by weight, more preferably 1 to 4 parts by weight, and polyolefin is 3 to 40 parts by weight, preferably Is preferably 4 to 20 parts by weight, more preferably 5 to 15 parts by weight, from the above viewpoint.

In the preferred ionomer composition described above, when an ionomer containing a divalent metal ion such as zinc, magnesium or calcium is used as an ion source, the above-mentioned characteristics can be easily expressed. Is preferable.
In consideration of moldability, mechanical properties, miscibility with other components, the melt flow rate at 190 ° C. under a load of 2160 g is 0.01 to 100 g / 10 minutes, particularly 0.1 to 50 g / 10 minutes. It is preferable to use one.

The olefin / glycidyl monomer copolymer constituting the preferred ionomer composition may be not only a binary copolymer of an olefin and a glycidyl monomer but also a multi-component copolymer containing other monomers. .
Examples of the olefin component in such a copolymer include ethylene, propylene, 1-butene and the like, and an ethylene copolymer is particularly preferable.

Examples of the glycidyl monomer include glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether, and 2-methylallyl glycidyl ether.
Furthermore, as the other monomer in the multi-component copolymer, for example, vinyl ester and unsaturated carboxylic acid ester are preferable, and specific examples of these other monomers include ethylene which is an ionomer base resin. -What was already illustrated as another monomer in an unsaturated carboxylic acid copolymer can be mentioned.

  In the olefin / glycidyl monomer copolymer, olefin is 50 to 99% by weight, particularly 52 to 98% by weight, glycidyl monomer is 0.5 to 20% by weight, particularly 1 to 18% by weight, It is preferable that the monomer is copolymerized in the range of 0 to 49.5% by weight, preferably 0 to 40% by weight.

Such a copolymer may be a random copolymer or a graft copolymer, but it is generally preferable to use a random copolymer in view of the uniformity of the reaction with the ionomer.
Such a random copolymer can be obtained, for example, by radical copolymerization at high temperature and high pressure.

  When an ethylene copolymer is used as the copolymer, the melt flow rate (MFR) at 190 ° C. and a load of 2160 g is 0.01 to 1000 g / 10 minutes, particularly 0.1 to 200 g / 10 minutes. Are preferably used.

Examples of the polyolefin constituting the preferred ionomer composition include polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and the like.
Among these, it is preferable to use polyethylene, especially linear low density polyethylene, or polypropylene, especially propylene / α-olefin copolymer.
In other words, by using linear low density polyethylene and propylene / α-olefin copolymer, it has excellent dispersibility with other components, design, heat resistance, abrasion resistance, scratch resistance, antifouling, mechanical A resin composition excellent in strength and the like can be easily obtained.

In particular, in the case of linear low density polyethylene, it is possible to obtain a composition that is excellent in compatibility with other resin components and hardly whitens with respect to bending.
The linear low density polyethylene is a copolymer of ethylene and an α-olefin having 3 or more carbon atoms, preferably 3 to 12, and having a density of 900 to 940 kg / m ³ , preferably 900 to 930 kg / m ³ . Is.
These are single-site catalysts such as a combination catalyst of a zirconium compound having a ligand having a cyclopentadienyl skeleton and an organoaluminum oxy compound catalyst component, or a highly active titanium catalyst component and an organoaluminum compound catalyst component. In the presence of a multi-site catalyst such as a combination catalyst, ethylene and an α-olefin having 3 or more carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-decene, It can be produced by copolymerizing dodecene, 4-methyl-1-pentene and the like.
The linear low density polyethylene has a melt flow rate (MFR) at 190 ° C. and 2160 g / load of 0.1 to 100 g / 10 min, particularly 0.2, in consideration of miscibility with other components and processability. It is preferable to use a product of ˜50 g / 10 minutes.

The propylene / α-olefin copolymer suitable as the polyolefin is a copolymer of propylene mainly composed of propylene and another α-olefin, and has a density of 870 to 930 kg / m ³ , particularly 880 to 920 kg / m ³ is preferable, and a melt flow rate (MFR) at 230 ° C. and 2160 g / load of 0.1 to 100 g / 10 min, particularly 0.2 to 80 g / 10 min is preferable.
As the α-olefin copolymerized with propylene, those having 2 to 12 carbon atoms, particularly 2 to 10 carbon atoms are preferable. Specifically, ethylene, 1-butene, 1-hexene, 1-octene, 1-octene, One type or two or more types such as decene, 1-dodecene, 4-methyl-1-pentene can be exemplified.

The propylene copolymer may be a random copolymer or a block copolymer.
A particularly suitable propylene random copolymer is a random copolymer of propylene and ethylene having a propylene content of 85 to 99.9% by weight, preferably 90 to 99.5% by weight, or propylene, ethylene and other α-olefins. A random copolymer consisting of
These are crystalline polymers copolymerized in the presence of a stereospecific catalyst.

The block copolymer is obtained by sequentially polymerizing or copolymerizing propylene and another α-olefin. Generally, (1) after polymerization of propylene, and (2) a copolymer of propylene and a little larger amount of α-olefin. It is carried out by combining one or more polymerization steps comprising polymerization and / or polymerization of (3) α-olefin.
In the polymerization of propylene (1), a small amount of α-olefin may be copolymerized, and in the polymerization of (3) α-olefin, a small amount of propylene may be copolymerized.
In any case, the block copolymer can be obtained by the multistage polymerization in the presence of a stereospecific catalyst.
A suitable propylene / α-olefin block copolymer is a block copolymer of propylene and ethylene containing about 60 to 95% by weight of the propylene polymer block (1).

The preferred ionomer composition can be obtained by melt-mixing the ionomer, olefin / glycidyl monomer copolymer, and polyolefin.
In melt mixing, a normal mixing device such as a screw extruder, a roll mixer, a Banbury mixer, or the like can be used.
Melt mixing can be carried out by blending the above three components at the same time. Most preferred is a method in which an olefin / glycidyl monomer copolymer and polyolefin are previously melt mixed and an ionomer is melt mixed.
According to this method, since the reaction with the ionomer does not occur locally by diluting the olefin / glycidyl monomer copolymer into the polyolefin, a composition having excellent properties can be produced with good quality stability. There are advantages.

Next, the constituent material of the adhesive resin layer in the laminated film of the present invention will be described.
In the present invention, the material constituting the adhesive resin layer is particularly limited as long as it is a resin that has good thermal adhesiveness to the substrate and can be adhered and laminated to the skin layer by, for example, coextrusion. Although it may be used as appropriate, it may be appropriately selected according to the type and nature of the base material used and the nature of the skin layer. However, the adhesive strength of 29 N / 25 mm or more (T Peel) is preferred.

  For example, when the base material to be bonded is a polyvinyl chloride resin sheet, it is an ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer resin layer, or the resin and other resins. Resin layers comprising a blend composition with further improving the processability and thermal adhesiveness of the adhesive resin layer, and these resin layers are particularly suitable from the viewpoint of high adhesive strength with the substrate. is there.

  When the base material is a polyolefin resin sheet, an ethylene / unsaturated carboxylic acid / (meth) acrylic acid alkyl ester copolymer resin, an olefin polymer resin modified with an unsaturated carboxylic acid or a derivative thereof. A resin layer comprising at least one selected from ethylene / (meth) acrylic acid alkyl ester copolymer resins and ethylene / vinyl acetate copolymer resins, or at least one of the resins and a resin other than those described above. The resin layer which consists of a blend composition with what further improves the workability of an adhesive resin layer and thermal adhesiveness can be mentioned, These resin layers are suitable from a viewpoint similar to the above.

  The ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer resin, which is one of the materials constituting the adhesive resin layer of the present invention, comprises ethylene, carbon monoxide, and (meth) acrylic acid alkyl ester. In the copolymer used in the present invention, the alkyl group in the (meth) acrylic acid alkyl ester component is linear or branched, and its carbon number is 1-18, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, isobutyl group, xyl group, 2 ethyl-hexyl group , Octyl groups and the like, and those having 2 to 8 carbon atoms are preferred.

  In this copolymer resin, ethylene is 30 to 90% by weight, preferably 40 to 80% by weight, carbon monoxide is 1 to 40% by weight, preferably 5 to 30% by weight, alkyl (meth) acrylate. It is desirable that the ester is contained in an amount of 5 to 60% by weight, preferably 20 to 50% by weight.

  In order to produce such a copolymer resin, each of the monomers ethylene, carbon monoxide, and (meth) acrylic acid alkyl ester is converted into t-butylperoxyisobutyrate or azoisobutyrate as a catalyst. A monomer may be copolymerized by supplying and mixing with nitrile at a predetermined ratio into a high-speed stirring reactor and stirring at high speed under high temperature and high pressure.

This ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer resin has a melt flow rate (MFR 190 ° C., 2160 g load) (based on JIS K7210-1999) of 1 to 1000 g / 10 min, more preferably 5 It is desirable that it is -200g / 10min.
The resin component blended with the ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer in order to further improve the workability and thermal adhesiveness of the adhesive resin layer includes ethylene / methacrylic acid copolymer. Examples include coalesced resins, ethylene / acrylic acid copolymer resins, ethylene / ethyl acrylate copolymer resins, ethylene / vinyl acetate copolymer resins, and among these, ethylene / methacrylic acid copolymer resins. An ethylene / acrylic acid copolymer resin is preferred.
A blend of these other resin components can be blended not only in one type but also in a plurality of types.
The blending amount is preferably 100 parts by weight or less (50% or less) in total with respect to 100 parts by weight of the ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer resin.

The ethylene / unsaturated carboxylic acid / (meth) acrylic acid alkyl ester copolymer resin, which is another material constituting the adhesive resin layer of the present invention, comprises ethylene, an unsaturated carboxylic acid, and (meth) acrylic acid. Consists of terpolymers of alkyl esters. The unsaturated carboxylic acid component in this terpolymer resin includes acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, monomethyl maleate, anhydrous A maleic acid etc. can be illustrated.
Among these, acrylic acid or methacrylic acid is particularly preferable.
In addition, the (meth) acrylic acid alkyl ester in the above-mentioned copolymer means an acrylic acid ester or a methacrylic acid ester, and specifically includes methyl, ethyl, n-butyl, isobutyl, 2-ethylhexyl, isooctyl. An ester such as can be exemplified.
The copolymer has an unsaturated carboxylic acid content of 1 to 15% by weight, particularly 2 to 12% by weight, and a (meth) acrylic acid ester content of 4 to 25% by weight, particularly 6 to 20% by weight. It is desirable that
Such a copolymer also has a melt flow rate (MFR) at 190 ° C. of 2160 g / load (according to JIS K7210-1999) of 0.5 to 100 g / 10 min, particularly 1 to 50 g / 10 min. Are preferred.
The copolymer resin can be obtained by radical copolymerization under high temperature and high pressure.

Other resin components blended with the copolymer resin to further improve the workability and thermal adhesiveness of the adhesive resin layer include ethylene / methyl (meth) acrylate and ethylene / (meth) acrylic acid. Ethyl etc. can be illustrated.
A blend of these other resin components can be blended not only in one type but also in a plurality of types.
The blending amount is preferably 100 parts by weight or less in total with respect to 100 parts by weight of the ethylene / unsaturated carboxylic acid / (meth) acrylic acid alkyl ester copolymer resin.

The ethylene / (meth) acrylate copolymer resin, which is another material constituting the adhesive resin layer of the present invention, is a copolymer of ethylene and (meth) acrylate, and the ester Examples of the component include esters such as methyl, ethyl, n-butyl, 2-ethylhexyl, and isooctyl.
Such a copolymer also preferably has a melt flow rate (MFR) at 190 ° C. and 2160 g / load of 0.5 to 100 g / 10 minutes, particularly 1 to 50 g / 10 minutes.
The (meth) acrylic acid ester component content is preferably 5 to 50% by weight.
Such a copolymer resin can be obtained by radical copolymerization under high temperature and high pressure.

Other resin components blended with the copolymer resin to further improve the workability and thermal adhesion of the adhesive resin layer include ethylene / (meth) acrylic acid copolymer resins and ethylene / acrylic acid. Examples thereof include an ethyl copolymer resin or polyethylene, and among these, an ethylene / (meth) acrylic acid copolymer resin and an ethylene / ethyl acrylate copolymer resin are preferable.
A blend of these other resin components can be blended not only in one type but also in a plurality of types.
The blending amount is preferably 100 parts by weight or less in total with respect to 100 parts by weight of the ethylene / (meth) acrylic ester copolymer resin.

  An olefin polymer modified with an unsaturated carboxylic acid or a derivative thereof, which is another material constituting the adhesive resin layer of the present invention, is obtained by converting a resinous or elastomeric olefin polymer into an unsaturated carboxylic acid. Alternatively, it is graft-modified or copolymer-modified with a derivative thereof.

The olefin polymer used as the base resin is an olefin homopolymer, a copolymer of two or more olefins, a copolymer of an olefin and a polar monomer, or the like.
Specifically, ethylene-based copolymers such as high, medium and low density polyethylene, ethylene / α-olefin copolymers, ethylene / unsaturated carboxylic acid ester copolymers; Examples thereof include propylene polymers such as a polymer, a propylene / α-olefin random copolymer, and a propylene / α-olefin block copolymer; poly-1-butene.

The elastomeric olefin polymer includes ethylene / α-olefin copolymer rubber such as ethylene / propylene copolymer rubber; propylene / α-olefin copolymer rubber, ethylene / propylene / diene copolymer rubber, and the like. Ethylene / α-olefin / diene copolymer rubber; block copolymer obtained by copolymerizing ethylene / propylene copolymer with polypropylene with controlled regularity; ethylene / methyl acrylate copolymer rubber; ethylene / acrylic acid Examples thereof include methyl / crosslinked site monomer copolymer rubber.
The α-olefin in each of the above copolymers is preferably one having about 2 to 12 carbon atoms.

The unsaturated carboxylic acid or its derivative grafted or copolymerized on the olefin polymer of the base polymer includes unsaturated carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, anhydrous Examples thereof include unsaturated carboxylic acid anhydrides such as maleic acid and itaconic anhydride.
The content of the graft monomer unit or copolymer monomer unit in the grafted or copolymerized olefin polymer is preferably 0.01 to 20% by weight, particularly preferably 0.1 to 20% by weight, based on the modified polymer. 5% by weight.

As the modified polymer, when the base resin is an ethylene polymer, the melt flow rate at 190 ° C. and 2160 g / load is 0.1 to 50 g / 10 minutes, particularly 0.2 to 10 g / 10 minutes. It is preferable to use one.
When the base resin of the modified polymer is a propylene polymer, the melt flow rate at 230 ° C. and 2160 g / load is 0.1 to 50 g / 10 minutes, particularly 0.2 to 10 g / 10 minutes. Is preferably used.

Resin components blended with the acid-modified olefin polymer resin to further improve the workability and thermal adhesion of the adhesive resin layer include ethylene / ethyl acrylate copolymer resin, ethylene vinyl acetate copolymer Examples thereof include a coalesced resin, polyethylene, and polypropylene. Among these, an ethylene / ethyl acrylate copolymer resin and an ethylene vinyl acetate copolymer resin are preferable.
A blend of these other resin components can be blended not only in one type but also in a plurality of types.
The blending amount is preferably 100 parts by weight or less in total with respect to 100 parts by weight of the acid-modified olefin polymer resin.

Next, an ethylene / vinyl acetate copolymer resin, which is yet another material constituting the adhesive resin layer of the present invention, is a copolymer of ethylene and vinyl acetate. The polymer component composition contains 95 to 50% by weight of ethylene, preferably 85 to 60% by weight, and 10 to 50% by weight of vinyl acetate, preferably 15 to 40% by weight.

The copolymer resin preferably has a melt flow rate of 0.01 to 500 g / 10 minutes, particularly 0.1 to 300 g / 10 minutes at 190 ° C. and 2160 g / load.
Other resin components blended with the copolymer resin in order to further improve the processability and thermal adhesiveness of the adhesive resin layer include commercially available α-olefin copolymers such as wax and tuffmer (trade name). Admer (trade name) which is a coalesced resin and adhesive polyethylene can be exemplified, and among these, tougher and admer are preferable.
A blend of these other resin components can be blended not only in one type but also in a plurality of types.
The blending amount is preferably 100 parts by weight or less in total with respect to 100 parts by weight of the ethylene / vinyl acetate copolymer resin.

  In the laminated film of the present invention, the adhesive resin layer does not necessarily have to be a single layer. The above-described ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer resin, ethylene / unsaturated carboxylic acid / (Meth) acrylic acid alkyl ester copolymer resin, olefin polymer resin modified with unsaturated carboxylic acid or derivative thereof, ethylene / (meth) acrylic acid alkyl ester copolymer resin, ethylene / vinyl acetate copolymer It can be composed of a plurality of layers selected from a coalesced resin, a composition thereof, and the like, and having different resin types.

  As such an adhesive resin layer composed of multiple layers, for example, an olefin polymer layer modified with an unsaturated carboxylic acid or a derivative thereof, and an ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer resin. A layer or two layers of a blend composition layer such as an ethylene / methacrylic acid copolymer resin or an ethylene / acrylic acid copolymer resin can be mentioned. It has the advantage that the adhesion with the layer is further improved.

  The method for producing the laminated film for the base material skin of the present invention from the above-described ionomer resin material for the skin layer and the resin material for the adhesive layer is not particularly limited, and it is formed and laminated using any known method. However, from the viewpoint of productivity and occupational hygiene and environmental considerations, a melt extrusion method that does not use an organic solvent-based adhesive is preferable, and in particular, a method of simultaneously forming a skin resin layer and an adhesive resin layer by coextrusion. preferable.

In addition, the thickness of the laminated film for the base material skin of the present invention is not particularly limited, and may be appropriately set according to its use and purpose. Polyolefins used for wall covering materials such as wallpaper and decorative sheets, When used for surface coating of a substrate such as polyvinyl chloride (usually about 300 mm to 30 μm), generally about 1 to 100 μm is preferable.
The thickness ratio of the skin layer / adhesive resin layer is preferably about 1:10 to 10: 1.

  For example, the method for laminating the above laminated film for a substrate skin on a wall paper by laminating it on a wallpaper or a polyolefin for decorative sheets or a polyvinyl chloride substrate is not necessarily limited to this. Is preferred.

An example of a suitable layer structure of the wall covering material of the present invention thus obtained will be shown.
The ethylene unsaturated carboxylic acid copolymer zinc ionomer skin layer is (a), and the a) ionomer composition skin layer of ionomer, olefin / glycidyl monomer copolymer and polyolefin is (b).
For polyolefin base sheet,
i) a) or b) skin layer / ethylene-ethyl acrylate copolymer resin layer / polyethylene or polypropylene base layer,
ii) a) or b) skin layer / ethylene ethyl acrylate copolymer graft acid modified layer / polyethylene or polypropylene base layer,
iii) a) or b) skin layer / ethylene-vinyl acetate copolymer resin layer / polyethylene or polypropylene substrate layer,
iv) a) or b) skin layer / ethylene / isobutyl acrylate / methacrylic acid copolymer resin layer / polyethylene or polypropylene base layer In the case of a polyvinyl chloride base sheet,
i) a) or b) skin layer / ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer resin layer / polyvinyl chloride substrate layer,

Next, the present invention will be described by way of examples.
"raw materials"
1) Ionomer for skin layer (a): Base resin: ethylene / methacrylic acid copolymer (methacrylic acid content 11% by weight), metal ion source: zinc, neutralization degree 63%, MFR: 5.0 g / 10 min 2 ) Ionomer composition for skin layer (b): 2 parts by weight of ethylene / glycidyl methacrylate copolymer (glycidyl methacrylate content: 12% by weight, MFR: 3.0 g / 10 min), propylene / ethylene random copolymer (polypropylene F232DC ( 15 parts by weight of Mitsui Chemicals Co., Ltd., density 900 kg / m ³ , MFR 9.0 g / 10 min (230 ° C.)) are melt-mixed in advance, and the obtained blend and 83 parts by weight of the ionomer (a) are melt-kneaded. Obtained ionomer composition 3) Resin for adhesive layer (1) Ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer resin (EnBACO) : Carbon monoxide content 10% by weight, n-butyl acrylate content 30% by weight, MFR 6.5 g / 10 min (190 ° C.)
4) Resin for adhesive layer (2) Acid-modified olefin polymer resin (EEA-g-MAH): ethyl acrylate content 25 wt%, maleic anhydride content 1.1 wt%, MFR 0.92 g / 10 min (190 ℃)
5) Resin for adhesive layer (3) Ethylene / unsaturated carboxylic acid / (meth) acrylic acid alkyl ester copolymer resin (EiBAMAA): isobutyl acrylate content 20 wt%, methacrylic acid content 4 wt%, MFR 12 g / 10 min (190 ° C)
6) Adhesive layer resin (4) Ethylene / (meth) acrylic acid alkyl ester copolymer resin (EEA): Ethyl acrylate content 25% by weight, MFR 5 g / 10 min (190 ° C.)
7) Resin for adhesive layer (5) Ethylene / vinyl acetate copolymer resin (EVA): vinyl acetate content 28% by weight, MFR 6 g / 10 min (190 ° C.)
8) Soft polyvinyl chloride (PVC) sheet: 0.1 mm thick
9) Polyolefin (PE) sheet: Low density polyethylene sheet, thickness 0.1 mm
10) Polypropylene resin sheet (for surface comparison): PP, thickness 0.1 mm
11) Polyester resin sheet (for surface comparison): PET-G, thickness 0.1 mm

"Evaluation methods"
Skin laminated film / base sheet adhesion strength: T-type peel test; tensile speed 300 mm / min, measurement temperature 23 ° C., test piece width 25 mm, n = 2 to 3,
Evaluation of test results ◎: Adhesive strength> 49N / 25mm
○: Adhesive strength 49-29N / 25mm
Δ: Adhesive strength 29-9.8N / 25mm
×: Adhesive strength 9.8-4.9N / 25mm
XX: Adhesive strength <4.9N / 25mm
Surface scratch resistance In accordance with JIS L0862, L0849, a Gakushin type abrasion test was carried out under the following conditions for evaluation.
A: No scratches can be confirmed in the sheet evaluation.
○: Unscratched part is 80% or more of the sheet surface △: Unscratched part is 50% or more and less than 80% of the sheet surface ×: Unscratched part is less than 50% of the sheet surface : Toyo Seiki abrasion tester Reciprocating speed: 60 times / minute Sliding piece: Cotton canvas No. 10 Reciprocating times: 100 times Load: 450 g (1.92 g / mm ² ) Sample form: 2 mm thickness
(Press sheet)
Measurement temperature: 23 ° C
Antifouling property In accordance with JIS A5705, A1454, the antifouling property was evaluated under the following conditions.
Sample: 0.15 mm thick sheet Contaminant: Lubricating oil, soybean oil, milk, soy sauce ◎ No swelling or discoloration by visual observation ○ Slight swelling or discoloration by visual observation × Heat resistance that swells and discolors by visual inspection The heat resistance was evaluated by heat-sealing the skin layers under the following conditions.
HS temperature 140 ° C, HS time 1 sec, HS pressure 0.2 MPa
◎ Peel without sealing ○ Slightly seal, but peels easily at the interface × Bending whitening that causes cohesive peeling or substrate breakage After the sheet is bent 180 °, it is returned to its original sheet shape The bent part was visually evaluated. ◎ The bent part cannot be visually determined. ○ The bent part remains slightly linear. × The chemical resistance that the bent part remains whitened: JIS A5705 conforming to A1454, observation; No change, A Small change, B Large change of glossiness: Gloss of film that was left in a gear oven heated to 180 (or 100) ° C. for 1 minute (or 30 minutes), then taken out from the gear oven and allowed to cool Measure the value and compare with the value before heating.
When the gloss value after heating is larger than the value before heating: ×, No change: ○
Optical property (surface gloss: incident angle 60 °): JIS Z8741
Yakan heat resistance: A stainless steel kettle containing 2 liters of heated boiling water is placed directly on the sheet and allowed to stand for 10 seconds, and then the adhesion to the sheet is evaluated.
What the kettle is fused to the sheet: ×, what the kettle can easily peel off from the sheet: ○

Example 1
Using two extruders, melt the ionomer for the skin layer (a) and the resin for the adhesive layer (1) (EnBACO), co-extrude from a 220 ° C T-die, cool and solidify, and base material with a thickness of 150 μm A heat-adhesive laminated film for skin (1a) was obtained (skin layer thickness 100 μm, adhesive resin layer thickness 50 μm).
Next, the laminated film (1a) is cut to a width of 25 mm, and is disposed so that the side of the adhesive resin layer of the film is in contact with the surface of the wallpaper base material PVC sheet, and thermocompression bonded at a temperature of 150 ° C. and a pressure of 0.098 MPa for 10 seconds. Thus, a PVC-based surface-coated wallpaper was obtained (surface-coated wallpaper 1a / PVC).
Next, using the same extruder as above, the ionomer composition for the skin layer (b) and the adhesive layer resin (1) (EnBACO) were melted, coextruded from a T die at 220 ° C., cooled and solidified, and the thickness was increased. A heat-adhesive laminated film (1b) for a substrate skin having a thickness of 150 μm was obtained (skin layer thickness 100 μm, adhesive resin layer thickness 50 μm).
Next, this laminated film (1b) was subjected to thermocompression bonding in the same manner as described above to obtain a PVC-coated surface-coated wallpaper (surface-coated wallpaper 1b / PVC).

(Example 2)
Using the same extruder as in Example 1, the ionomer composition for the skin layer (b) and the resin for the adhesive layer (2) (EEA-g-MAH) were melted and coextruded from a T die at 220 ° C. and cooled. Solidified to obtain a heat-adhesive laminated film (2b) for substrate skin having a thickness of 150 μm (skin layer thickness 100 μm, adhesive resin layer thickness 50 μm).
Next, this laminated film (2b) is cut into a width of 25 mm, and is disposed so that the side surface of the adhesive resin layer of the film is in contact with the surface of the wallpaper substrate PO (polyethylene PE), and is 10 at a temperature of 150 ° C. and a pressure of 0.098 MPa. The surface-coated wallpaper (2b / PE) of a polyethylene base was obtained by thermocompression bonding for 2 seconds.

(Example 3)
In Example 2, the laminated film (3b) and the surface-coated wallpaper (in the same manner as in Example 2 except that the adhesive layer resin (2) (EEA-g-MAH) was changed to (3) (EiBAMAA) 3b / PE) was obtained.

Example 4
In Example 2, the laminated film (4b) and the surface-coated wallpaper (in the same manner as in Example 2 except that the adhesive layer resin (2) (EEA-g-MAH) was changed to (4) (EEA) 4b / PE) was obtained.

(Example 5)
In Example 2, the laminated film (5b) and the surface-coated wallpaper (in the same manner as in Example 2 except that the adhesive layer resin (2) (EEA-g-MAH) was changed to (5) (EVA)) 5b / PE) was obtained.

(Example 6)
The laminated films obtained in Examples 1 to 5 (6 samples of 1a, 1b to 5b) were subjected to relative comparison under the same conditions for surface scratch resistance, surface antifouling property, heat resistance, bending whitening property, and weather resistance. evaluated.
For comparison, the same PVC sheet, PE sheet, commercially available polyester resin film, and commercially available polypropylene film as the base material were comparatively evaluated under the same conditions.
Furthermore, the adhesive strength of the coated wallpaper (6 samples of 1a / PVC, 1b / PVC, 2b / PE to 5b / PE) was measured and evaluated.
The evaluation results are summarized in Table 1.

(Example 7)
The chemical resistance of the heat-adhesive laminated film (2b) for the substrate skin used in Example 2 was evaluated.
The results are shown in Table 2.

(Example 8)
The wallpaper of Example 5 (layer structure: b / EVA / PE) was evaluated for gloss return and kettle heat resistance.
The results are shown in Table 3.

Claims (9)

  A skin layer comprising an ionomer based on an ethylenically unsaturated carboxylic acid copolymer or a multi-component copolymer containing ethylene and an unsaturated carboxylic acid as main constituent units, or a composition containing the ionomer as a main blending component A heat-adhesive laminated film for a substrate skin, comprising an adhesive resin layer having good thermal adhesion to a substrate on one surface.   The laminated film according to claim 1, which is for surface coating of a wall covering base material.   The laminated film according to claim 1 or 2, wherein the skin layer is an ionomer composition layer comprising the ionomer, an olefin / glycidyl monomer copolymer, and a polyolefin.   The laminated film according to any one of claims 1 to 3, wherein the adhesive resin layer has an adhesive strength of 29 N / 25 mm or more to a substrate to be thermally bonded.   In the case where the base material to be thermally bonded is a polyolefin resin sheet, the adhesive resin layer is composed of an ethylene / unsaturated carboxylic acid / (meth) acrylic acid alkyl ester copolymer resin, an unsaturated carboxylic acid or its A resin layer comprising at least one selected from an olefin polymer resin modified with an acid derivative, an ethylene / (meth) acrylic acid alkyl ester copolymer resin, and an ethylene / vinyl acetate copolymer resin; A resin layer comprising a blend composition of at least one resin other than the above and further improving the processability and thermal adhesiveness of the adhesive resin layer, and the base material to be thermally bonded is polyvinyl chloride In the case of a resin-based resin sheet, the adhesive resin layer is an ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer resin layer, or The resin and laminated film according to claim 4, wherein the other processing of a resin adhesive resin layer is a resin layer comprising a blend composition as causing a thermal adhesive further improved.   The laminated film according to claim 1, wherein the adhesive resin layer comprises a plurality of layers having different resin types.   A wall covering material obtained by thermally bonding the laminated film according to any one of claims 1 to 6 to a resin substrate surface.   The resin substrate is a soft polyvinyl chloride resin sheet, and the adhesive resin layer of the laminated film is a resin layer made of ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer resin. Wall covering.   The resin base material is a polyolefin resin sheet, and the adhesive resin layer of the laminated film is acid-modified with an ethylene / unsaturated carboxylic acid / (meth) acrylic acid alkyl ester copolymer resin, an unsaturated carboxylic acid or a derivative thereof. The wall covering material according to claim 7, which is a resin layer comprising at least one kind selected from an olefin polymer resin, an ethylene / (meth) acrylic acid alkyl ester copolymer resin, and an ethylene / vinyl acetate copolymer resin.