JPH06297654A - Laminated film and its use - Google Patents

Abstract

PURPOSE:To obtain a laminated film which can be laminated thermally at low temperature and can be embossed with an anti-fouling function by arranging a specific vinyl chloride copolymer composition layer and a specific ethylene/ fatty acid vinyl copolymer saponification layer. CONSTITUTION:The laminated film is composed of a specific vinyl chloride copolymer composition layer and an ethylene/fatty acid vinyl copolymer saponification layer. The vinyl chloride copolymer composition layer is composed of 100 pts.wt. of a vinyl chloride copolymer which contains 60 to 99mol% of vinyl chloride component and 1 to 40mol% of vinyl acetate component and/or a carboxylic acid component, and 0.1 to 15 pts.wt. of a chemical compound containing at least two isocyanate groups. On the other hand, the ethylene/fatty acid vinyl copolymer saponification layer consists of 20 to 65mol% of ethylene and at least 90mol% of fatty acid vinyl component in terms of a degree of sponification. Consequently, the laminated film has an anti-fouling function and can be embossed easily.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film having a stain-proofing function which can be heat-laminated at a low temperature and can be easily embossed, and a wallpaper or a decorative board having the laminated film.

[0002]

2. Description of the Related Art Conventionally, wallpaper containing a polyvinyl chloride resin layer is known. However, wallpaper containing these polyvinyl chloride resin layers, and decorative boards used for ceiling materials, wall materials, floor materials, etc. for general households, hospitals, clinics, restaurants, factories, ships, trains, automobiles, etc. Are easily contaminated with cigarette smoke, hand dust, graffiti, and pigments in various foods. Also, the plasticizer for polyvinyl chloride resin bleeds on the surface of the wallpaper. Dust adheres to the bleeding plasticizer, and the PVC wallpaper becomes more easily soiled.

As disclosed in JP-A-58-23973, there is known a stain resistant wallpaper in which an acrylic resin film is laminated on a vinyl chloride wallpaper. However, although these wallpaper are excellent in stain resistance as compared with non-laminated PVC wallpaper, it is difficult to say that they are perfect, and there is a problem that the tendency becomes large especially when a long time has passed after lamination. Further, the acrylic resin film is inferior in chemical resistance and is particularly apt to be attacked by esters, ketones, aromatic compounds and the like, and therefore it is necessary to pay attention to wiping off stains, which is not satisfactory.

As disclosed in Japanese Utility Model Publication No. 59-172797, a stain-resistant wallpaper is known in which a film of a saponified product of an ethylene-fatty acid vinyl copolymer (hereinafter referred to as EVOH) is laminated on a vinyl chloride wallpaper. There is. This wallpaper has excellent chemical resistance and plasticizer barrier properties, and has better stain resistance than non-laminated PVC wallpaper. Further EVO
The H film has a relatively small electric resistance and is less likely to be charged with static electricity, and therefore has an advantage that dust is not easily attached to the surface of the wallpaper. However, a urethane adhesive is used in the above-mentioned Jitsukaisho, and the coating amount is as large as 15 g / m 2 and it is uneconomical.

JP-A-60-224542 and JP-A-62-15265 disclose that EVOH is excellent in blocking the plasticizer for polyvinyl chloride resin, and EVOH is a plasticizer for polyvinyl chloride resin. It is described that it is used for blocking. However, the above-mentioned Japanese Patent Laid-Open Publication No. Sho-A is related to the solution coating method and the dry laminating method and does not describe the thermal laminating method.

JP-A-60-239233 and JP-A-60-242053 describe a film for thermal lamination of EVOH. However, in the film of JP-A-60-239233, the reactive polyurethane polymer containing an expensive isocyanate group is used in the adhesive layer, and the ratio of the reactive polyurethane polymer containing an isocyanate group is 17 to 150% by weight. It is uneconomical because it is high, and it does not show sufficient adhesive strength at 120 ° C. or less during thermal lamination, and it is processed at a high temperature of 125 ° C. or more in Examples, and is relatively flexible like a PVC sheet. There is no problem with the base material, but the operability is poor in the case of laminating with a base material such as foamed vinyl chloride wallpaper which is not particularly stiff. on the other hand,
JP-A-60-242053 is uneconomical because the processing step is long because the adhesive has two layers.

JP-A-4-131236 discloses a vinyl chloride polymer composition of a laminate comprising a layer of a composition comprising EVOH and a polyolefin and a layer of a composition comprising a vinyl chloride polymer and an isocyanate-urethane compound. It is described that the above layer is used as a sealing layer and is used as an easily openable container. However, the above-mentioned Japanese Patent Application Laid-Open No. Hei hei demands easy opening property, that is, low sealing strength, and there is no description regarding strong lamination such as wallpaper, and no description regarding expansion to wallpaper.

[0008]

DISCLOSURE OF THE INVENTION As described above, a laminated film having a stain prevention function that is inexpensive, can be heat-laminated at a low temperature, and can be easily embossed, and a vinyl chloride wallpaper laminated with the laminated film. Or there is a strong demand for veneer.

The present invention, however, was conceived in order to solve the above-mentioned drawbacks of the prior art, and is inexpensive and has the barrier property of the plasticizer for polyvinyl chloride resin, the antifouling function and the like. Another object of the present invention is to obtain a laminated film which can be heat-laminated at a low temperature and can be easily embossed, and a vinyl chloride wallpaper or a decorative board in which the laminated film is laminated.

[0010]

The above object is to provide an EVO having barrier properties and stain resistance of a plasticizer for polyvinyl chloride resin.
By laminating a specific adhesive composition on the H layer or the resin composition layer containing EVOH, and also by laminating the laminated film on at least one side of a substrate, particularly a polyvinyl chloride resin layer containing a plasticizer, particularly This is accomplished by providing a laminate laminated to the outer layer.

In the present invention, the vinyl chloride copolymer is a vinyl chloride component in an amount of 60 to 99 mol%, preferably 7%.
It is a substance containing 0 to 95 mol%, a vinyl acetate component and / or a carboxylic acid component alone or in total of 1 to 40 mol%, preferably 5 to 30 mol%. Examples of the carboxylic acid component include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, their mono- or diesters, their anhydrides, or monocarboxylic acid vinyl esters, such as acrylic acid, methacrylic acid, and maleic acid. Examples thereof include acid, itaconic acid, methyl acrylate, methyl methacrylate, maleic acid monoester, maleic acid diester, itaconic acid monoester, itaconic acid diester, maleic anhydride, itaconic anhydride, vinyl stearate and the like. These carboxylic acid components can be used either as a random copolymerization component or as a graft copolymerization component. Representative vinyl chloride copolymers include vinyl chloride-vinyl acetate copolymers, vinyl chloride-methacrylic acid (methyl) copolymers,
Vinyl chloride-vinyl stearate copolymer, vinyl chloride-vinyl acetate-methacrylic acid (methyl) copolymer, vinyl chloride-vinyl acetate-acrylic acid (methyl) copolymer,
Examples thereof include vinyl chloride-vinyl acetate-maleic acid (ester) copolymers and vinyl chloride-vinyl acetate-maleic anhydride copolymers. In addition, vinyl chloride-vinyl acetate-
The carboxylic acid (ester) copolymer may be a terpolymer or higher terpolymer, or a carboxylic acid (ester) may be graft-modified on a terpolymer or higher terpolymer such as a vinyl chloride-vinyl acetate copolymer. It can be a thing. These may be used alone, or a mixture of two or more kinds of compounds may be used.

In the present invention, the compound containing two or more isocyanate groups means tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5- Naphthylene diisocyanate, 4,
Compounds such as 4'-dicyclohexylmethane diisocyanate, compounds obtained by polycondensation by condensation reaction of the above-mentioned compound containing two or more isocyanate groups with water, and three compounds by thermal reaction of the above-mentioned compound containing two or more isocyanate groups. All the hydroxyl groups of the quantified compound and polyols such as trimertylolpropane, glycerin, and pentaerythritol are converted to the above isocyanate groups by 2
A compound reacted with a compound containing one or more is preferable. These may be used alone, or a mixture of two or more kinds of compounds may be used. A compound obtained by reacting all hydroxyl groups of a polyol such as propylene glycol, ethylene glycol, polypropylene glycol having an average molecular weight of 200 to 5000, and polyethylene glycol having an average molecular weight of 200 to 2000 with a compound containing two or more of the above isocyanate groups, and isophthalic acid. , Succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid containing at least two isocyanate groups in the functional group of a polyester having an average molecular weight of 3,000 or less containing at least one dicarboxylic acid component selected from the constituents. You may use together the compound etc. which were made to react with a compound. (These are CN
Abbreviated).

In the present invention, the ratio of the vinyl chloride copolymer to CN is 0.01 to 15 parts by weight, preferably 0.5 to 100 parts by weight, based on 100 parts by weight of the vinyl chloride copolymer.
The amount is 10 parts by weight, more preferably 1 to 5 parts by weight. CN
Is less than 0.01 part by weight, the adhesive strength to the EVOH composition film may be insufficient, and if it exceeds 15 parts by weight, the resulting laminated film may be blocked during storage and the embossability is deteriorated. It is easy, and at the temperature of 120 ° C. or less at the time of heat lamination, it does not show sufficient adhesive force.

In the present invention, the method of blending the vinyl chloride copolymer composition is not particularly limited, and the method of directly blending the vinyl chloride copolymer and CN, or blending the solution of the vinyl chloride copolymer with CN. Examples thereof include a method of blending, a method of blending a solution of CN with a vinyl chloride-based copolymer, a method of blending a solution of vinyl chloride-based copolymer with a solution of CN, and the like. After blending, it is desirable to use up within 1 day, more preferably within 16 hours.

The solvent is not particularly limited as long as it does not contain active hydrogen such as a hydroxyl group and an amino group, and can dissolve the vinyl chloride copolymer and CN and can be easily dried. Methyl ethyl ketone, methyl butyl Examples include ketones, acetone, ethyl acetate, butyl acetate, benzene, toluene, hexane, tetrahydrofuran, and the like, or a mixed solvent of one or more of these may be used.

The vinyl chloride-based copolymer composition contains an antioxidant, a slip agent, a colorant, an antibacterial agent, a deodorant, an ultraviolet absorber, a lubricant, and a polyurethane, a polyester, within a range not impairing the present invention. An adhesive for dry laminating or extrusion laminating such as polyether may be blended.

In the present invention, the thickness of the vinyl chloride copolymer composition layer is not particularly limited, but is preferably 0.5-.
The thickness is 10 μm, more preferably 1 to 6 μm, still more preferably 1 to 4 μm. If it is less than 0.5 μm, the adhesive force between the EVOH layer or EVOH composition layer and the polyvinyl chloride resin layer containing a plasticizer tends to be low, and if it exceeds 10 μm, the cost becomes high, which is not preferable.

In the present invention, by using a resin composition prepared by blending EVOH with a carboxylic acid-modified polyethylene resin (hereinafter abbreviated as CPE), the adhesive force between the composition layer and the vinyl chloride copolymer composition layer is improved. Not only is it improved, but embossing is even easier when laminated with wallpaper. By using the composition layer, the surface glossiness of at least one surface of the composition layer (Murakami gloss meter, measured at an incident light angle of 75 °) can be made to be 40% or less, and the glossiness can be improved. It is possible to obtain a PVC wallpaper with excellent erasing ability and to give a high-class feeling. The blending ratio of EVOH and CPE is 95 to 50% by weight of EVOH and 5 to 50% by weight of CPE, preferably 92 to 55% by weight of EVOH and CPE8.
~ 45% by weight. If the CPE content is less than 5% by weight, the glossiness is not satisfied, and if it exceeds 50% by weight, the plasticizer barrier property is poor, the film-forming property is deteriorated, and the film has holes. Furthermore, the melt index (hereinafter referred to as MI) of EVOH and CPE measured under the conditions of a temperature of 190 ° C. and a load of 2.16 kg according to ASTM D 1238.
Where MIa and MIb respectively, 3 ≦ MIa / MIb ≦
A good matte layer is obtained in the range of 80. 19
If MI cannot be measured at 0 ° C, extrapolation is required.

Here, CPE is a polyethylene resin modified with α, β-unsaturated carboxylic acid or the carboxylic acid anhydride or carboxylic acid ester, and α, β
-Unsaturated carboxylic acid or said carboxylic anhydride or carboxylic acid ester content is 0.0005 to 5 mol%, preferably 0.001 to 1 mol%, more preferably 0.0
It is from 01 to 0.4 mol%. If it is less than 0.0005 mol%, the dispersibility becomes poor at the time of blending with EVOH, and the matte effect of the film is poor. It is desirable that all polyethylene resins are modified with α, β-unsaturated carboxylic acid or the carboxylic acid anhydride or carboxylic acid ester, but a high concentration carboxylic acid modified polyethylene resin seed polymer and unmodified polyethylene resin The final modified amount of the blend may be within the above range. The α, β-unsaturated carboxylic acid or the carboxylic acid anhydride or carboxylic acid ester means acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, acrylic acid ester, methacrylic acid ester, maleic acid. Examples thereof include acid mono- or diesters and itaconic acid mono- or diesters, with maleic anhydride being preferred. Examples of the polyethylene resin include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ethylene-based copolymers (ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, etc.) Density polyethylene is preferred.

The EVOH having an ethylene content of 20 to 65 mol%, preferably 25 to 60 mol% and a degree of saponification of the fatty acid vinyl component of 90 mol% or more, preferably 95 mol% or more is suitable. used. If the ethylene content is less than 20 mol%, the water resistance is poor and the embossability is also poor. If it exceeds 65 mol%, the oil resistance tends to be poor, and oily contaminants are likely to permeate, resulting in poor stain resistance, which is not preferable. Even if the degree of saponification of the fatty acid vinyl component is less than 90 mol%, the oil resistance is poor, and oily contaminants easily permeate. Examples of the fatty acid vinyl used as a raw material for EVOH include vinyl acetate, vinyl pivalate, and vinyl benzoate.
Vinyl acetate is preferred. Propylene in this EVOH,
Comonomer components other than ethylene and fatty acid vinyl, such as N-vinylpyrrolidone, can be used within a range that does not impair the object of the present invention.

EVOH may be a composition of two or more kinds of EVOH having different ethylene contents, saponification degrees and polymerization degrees, and boric acid, an antioxidant,
Slip agent, colorant, antibacterial agent, deodorant, ultraviolet absorber,
A thermoplastic resin such as a lubricant or polyamide may be blended.

In the present invention, as a method of obtaining a resin composition comprising EVOH and CPE, a twin screw extruder, a Brabender plastograph, etc. are used in advance for melt-blending pelletization, followed by a T-die method or an inflation method. There is a method of forming a film by a melt extrusion method, or a method of directly forming a dry blend pellet into a film by a melt extrusion method such as a T-die method or an inflation method.

In the present invention, the EVOH layer or EV
The thickness of the resin composition layer of OH and CPE is not particularly limited, but is preferably 10 to 30 μm, and if it is less than 10 μm, pinholes are likely to occur in the film layer during embossing, which is a plasticizer for polyvinyl chloride resin. The blocking property of the drug deteriorates. If it exceeds 30 μm, the laminated wallpaper becomes hard and the work during construction becomes difficult to perform, which is not preferable.

In the present invention, the method for producing the laminated film is not particularly limited, but a method of coating a film made of a resin composition of EVOH and CPE with a solution of a vinyl chloride copolymer composition is preferable. What is important for strengthening the adhesive force between the film made of the resin composition and the vinyl chloride copolymer composition layer is that when laminating the vinyl chloride copolymer composition on the film made of the resin composition, isocyanate is used. Although the group needs to remain, it is necessary that the isocyanate group reacts and disappears during thermal lamination with a vinyl chloride wallpaper or the like. The method of eliminating the isocyanate group is such that, immediately after lamination,
It is achieved by storing at a temperature of ° C for 16 hours or more.

In the present invention, a wallpaper containing a polyvinyl chloride resin layer containing a plasticizer means a polyvinyl chloride resin on a support made of flame-retardant paper, non-woven fabric, glass fiber, asbestos paper or the like. Agents, if necessary, a composition containing a pigment, a filler, a stabilizer, etc., laminated by a calendar method, a coating method, etc., and further, a product obtained by subjecting these laminated materials to a printing process, or foaming. Examples of the final product include polyvinyl chloride resin foamed 1.5 to 15 times by blending the agent. In the present invention, the decorative plate is a generic term for a printed decorative plate, a decorative gypsum board, a vinyl chloride decorative plate, a vinyl chloride steel plate, a vinyl chloride incombustible plate and the like. The printed decorative board is a product obtained by printing thin paper or the like and laminating it on a support made of plywood, particle board or the like. In addition, embossing may be applied to emphasize the three-dimensional effect. Also makeup gypsum board,
PVC decorative plate, PVC steel plate, PVC incombustible plate, etc. are printed on a polyvinyl chloride resin sheet containing a plasticizer, etc., and are supported by gypsum board, particle board, plywood, steel plate, concrete plate, etc. It is one that is laminated to the body. As with the printed decorative board, embossing may be applied to enhance the three-dimensional effect.

In the present invention, the plasticizer for polyvinyl chloride resin is liquid at 20 ° C., and is 20 to 7 relative to the total weight.
5% by weight is contained. As a plasticizer which is liquid at 20 ° C., dibutyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, diisodecyl phthalate,
Phthalic acid ester plasticizers such as didecyl phthalate, dinonyl phthalate, butyllauryl phthalate, dilauryl phthalate and butylbenzyl phthalate, tricresyl phosphate, tributyl phosphate, phosphoric acid esters such as tri-2-ethylhexyl phosphate Examples include plasticizers and chlorine-containing plasticizers such as chlorinated paraffin. The target laminate can be obtained by laminating the layer of the composition of the present invention on at least one surface of the polyvinyl chloride resin layer containing one or more of these plasticizers, particularly on the outermost layer.

In the present invention, the temperature of thermal lamination of the laminated film and the vinyl chloride wallpaper is preferably 70 to 180.
C., more preferably 80 to 160.degree. C., still more preferably 100 to 150.degree. If the temperature is lower than 70 ° C., the adhesive force may not be easily expressed, and the embossing for enhancing the three-dimensional effect may be difficult. If the temperature exceeds 180 ° C, the resin composition layer on the outer surface of the laminated film may partly melt and the tackiness may appear, or the glossiness may deteriorate, and the foamed PVC layer may be affected by the pressure during thermal lamination. It is compressed and the reproducibility of embossing deteriorates.

The laminate of the present invention thus obtained is
It can be heat-laminated at low temperature, can be easily embossed, has no change in the laminate strength even after long-term use, and maintains the stain-preventing function, and is very useful as a wallpaper or decorative board.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[0030]

【Example】

Example 1 EVOH having an ethylene content of 44 mol% and a saponification degree of a vinyl acetate component of 99.5 mol% (MI 5.5 g / 10
Min) 75 wt% and maleic anhydride graft modified high density polyethylene resin (MI 0.3 g / 10 min) 25 wt% are blended and pelletized at 210 ° C. using a twin screw extruder, and a single screw extruder. Was used to obtain a film of a resin composition having a thickness of 20 μm at 210 ° C. The glossiness of the obtained film was as good as 21%.

A vinyl chloride copolymer composition comprising 100 parts by weight of a vinyl chloride copolymer containing 87 mol% of a vinyl chloride component and 13 mol% of a vinyl acetate component and 1.5 parts by weight of hexamethylene diisocyanate was added to methyl ethyl ketone. :
Immediately after dissolving in a mixed solvent of toluene = 1: 1 so as to have a solid content concentration of 20% by weight, the above film was immediately coated with a gravure coater to a coating amount of 2 g / m ↑ 2 (based on solid content), It was dried at 70 ° C. for 4 minutes to obtain a laminated film. This laminated film was stored in a roll form at 35 ° C. for 2 days to eliminate isocyanate groups. No blocking occurred during storage at 35 ° C.

On the other hand, a flame-retardant paper for backing impregnated with 24 parts by weight of a guanidine sulfamate flame retardant per 100 parts by weight of paper, 100 parts by weight of polyvinyl chloride resin, 50 parts by weight of a filler, and a plasticizer (ftar). 55 parts by weight of (di-2-ethylhexyl acid), 20 parts by weight of pigment, 3 parts by weight of flame retardant, 2 parts by weight of stabilizer, and 2 parts by weight of foaming agent are laminated, and then vinyl chloride is foamed to form a vinyl chloride wallpaper. Got

The surface of the vinyl chloride copolymer composition and the surface of the polyvinyl chloride resin laminated on the paper are put together, press-bonded with a hot embossing roll at 110 ° C. and simultaneously embossed,
I got a PVC wallpaper with a stain prevention function. The peripheral portion of the concave portion of the embossing roll was also faithfully reproduced as the peripheral portion of the convex portion of the wallpaper, and the reproducibility of embossing was good.

The adhesive strength of the vinyl chloride wallpaper was measured by T-type peeling, and it was found that the polyvinyl chloride layer was broken and had a sufficient adhesive strength. The adhesive strength of the above wallpaper was measured by T-type peeling after standing at room temperature for 50 days. However, the polyvinyl chloride layer was completely destroyed and no decrease in adhesive strength due to the plasticizer was observed.

In order to examine the barrier property of the plasticizer for polyvinyl chloride resin, a 6 cm × 6 cm 70 μm thick non-plasticized polyvinyl chloride film was adhered to the EVOH surface of the wallpaper, and the non-plasticized polyvinyl chloride film was adhered. Then, a load of 3 kg was applied and the mixture was allowed to stand at 70 ° C. for 7 days, and the weight change of the non-plasticized polyvinyl chloride film was examined. No increase in weight was observed, and no stickiness on the EVOH surface was observed. The prevention of migration of plasticizer was perfect.

The atmospheric temperature in the above test is so high that it is not usually experienced in daily life, and it is generally said that it has a permeation rate of about 50 times room temperature. The fact that the potency is maintained even under these conditions means that it can withstand long-term use.

In order to check the stain prevention function, the EV of the wallpaper
Oily red ink (Mitsubishi Marker manufactured by Mitsubishi Pencil Co., Ltd.) and soy sauce (Kikkoman dark mouth manufactured by Kikkoman Co., Ltd.) were applied to the OH surface in a size of 2 cm × 2 cm, and wiped off with gauze with benzine after 24 hours. But no trace was left. In addition, even if it was wiped off with a gauze moistened with a neutral detergent, no trace was left in the case of soy sauce, and the surface was not damaged by water, confirming that it has sufficient water resistance. As shown in, the stain prevention function was perfect.

Comparative Example 1 Example 1 was repeated except that the amount of hexamethylene diisocyanate in Example 1 was changed to 1.5 parts by weight and 4,4'-dicyclohexylmethane diisocyanate was changed to 50 parts by weight.
However, blocking occurred during storage of this laminated film in a roll form at 35 ° C. for 2 days, and the subsequent tests had to be stopped.

Example 2 In Example 1, vinyl chloride copolymer 100 containing 87 mol% of vinyl chloride component and 13 mol% of vinyl acetate component.
Chloride containing 85 mol% of vinyl chloride component and 15 mol% of vinyl acetate component and maleic anhydride component in total instead of vinyl chloride copolymer composition of 1 part by weight and 1.5 parts by weight of hexamethylene diisocyanate. A vinyl chloride copolymer composition of 100 parts by weight of a vinyl copolymer and 3 parts by weight of 4,4′-diphenylmethane diisocyanate was used, and the procedure of Example 1 was repeated except that the composition was stored at 40 ° C. for 1 day. The barrier properties and antifouling function of the plasticizer were similarly tested.
The results are shown in Table 1, and all the effects were good.

Example 3 EVOH (MI: 1.5 g / 10) having an ethylene content of 32 mol% and a saponification degree of a vinyl acetate component of 99.6 mol%.
Min) 70% by weight and maleic anhydride graft modified high density low density polyethylene resin (MI 0.5 g / 10 min)
Using a resin composition consisting of 30% by weight, blend pelletizing at 220 ° C. using a twin-screw extruder, and using a single-screw extruder at 220 ° C., a thickness of 15 μ
A film composed of the resin composition of m was obtained. The glossiness of the obtained film was as good as 25%. The following is Example 1
The test was performed according to The results are shown in Table 2, and all the effects were good.

Comparative Example 2 A polyester obtained from ethylene glycol, terephthalic acid and isophthalic acid having hydroxyl groups at both ends and a compound of glycerin and xylylene diisocyanate were mixed at 1: 1.2.
A reaction type polyurethane was obtained by reacting at (molar ratio of hydroxyl group and isocyanate group). A laminated film was obtained in the same manner as in Example 3, except that 20 parts by weight of reactive polyurethane was used instead of 1.5 parts by weight of hexamethylene diisocyanate. The results are shown in Table 2, but the reproducibility of embossing was insufficient in the peripheral portion of the convex portion of the wallpaper, which corresponds to the peripheral portion of the concave portion of the embossing roll.

Example 4 A laminated film was obtained in the same manner as in Example 1, except that the EVOH-only film was obtained without adding the maleic anhydride graft-modified high-density polyethylene resin.
The following was carried out and tested according to Example 1. The results are shown in Table 2, and all the effects were good.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

The laminated film of the present invention can be heat-laminated at a low temperature and can be easily embossed, and the wallpaper laminated with the laminated film can maintain the stain prevention function for a long period of time.

Claims (3)

[Claims] 1. A compound 0 containing 100 parts by weight of a vinyl chloride-based copolymer containing 60 to 99 mol% of a vinyl chloride component and 1 to 40 mol% of a vinyl acetate component and / or a carboxylic acid component, and two or more isocyanate groups. 1 to 15 parts by weight of a vinyl chloride copolymer composition layer and an ethylene-fatty acid vinyl copolymer saponified product having an ethylene content of 20 to 65 mol% and a fatty acid vinyl component saponification degree of 90 mol% or more. Laminated film having layers. 2. A compound 0 containing 100 parts by weight of a vinyl chloride copolymer containing 60 to 99 mol% of a vinyl chloride component, 1 to 40 mol% of a vinyl acetate component and / or 1 to 40 mol% of a carboxylic acid component, and two or more isocyanate groups. 1 to 15 parts by weight of a vinyl chloride copolymer composition layer and an ethylene-fatty acid vinyl copolymer saponified product having an ethylene content of 20 to 65 mol% and a fatty acid vinyl component saponification degree of 90 mol% or more. A laminated film having a resin composition layer comprising 95 to 50% by weight and a carboxylic acid-modified polyethylene resin of 5 to 50% by weight. 3. A wallpaper or decorative board in which the vinyl chloride copolymer composition layer side of the laminated film according to claim 1 or 2 is laminated on at least one surface of a polyvinyl chloride resin layer containing a plasticizer.