JPH08258229A - Laminated film and its use - Google Patents

Abstract

PURPOSE: To realize thermal lamination at low temperature, and facilitate embossing by a structure wherein the laminated film has the specified vinyl chloride copolymer composition layer and polyalcohol layer, which is obtained by reducing polyketone consisting of carbon monoxide-ethylene copolymer. CONSTITUTION: The laminate film has vinyl chloride copolymer composition layer and polyalcohol layer, which is obtained by reducing polyketone consisting of carbon monoxide-ethylene copolymer. The vinyl chloride copolymer composition consists of 100 pts.wt. of vinyl chloride copolymer containing 60-99mol.% of vinyl chloride component, 1-40mol.% of vinyl acetate component and/or carboxylic acid component singly or in sum and 0.1-15 pts.wt. of compound (CN) containing two or more isocyanate group. If CN is below 0.1 pts.wt., the adhesion to the polyalcohol layer is weak. If CN exceeds beyond 15 pts.wt., the laminated film tends to block during storage and embossing characteristics deteriorate and no sufficient adhesion is shown by thermal lamination at low temperature.

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 an antibacterial property which can be heat-laminated at a low temperature and can be easily embossed, or has a deodorant and stain preventing function, 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 wallpapers have excellent stain resistance compared to non-laminated PVC wallpaper, they are not perfect, and there is a problem that the tendency becomes large especially when a long period of 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 is more excellent in 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, which 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.

On the other hand, Japanese Patent Application Laid-Open No. 4-173244 describes an antibacterial plastic multilayer film characterized in that the outermost layer and / or the innermost layer of the plastic multilayer film is a film layer containing an inorganic antibacterial substance. is there. However, the above-mentioned Japanese Patent Laid-Open No. Heihei does not describe the incorporation of a specific antibacterial agent into EVOH, and does not describe anything about appliances and building materials.

On the other hand, Japanese Unexamined Patent Publication (Kokai) No. 61-28082 describes a deodorant wallpaper obtained by coating or incorporating a composition in which an iron (II) compound and L-ascorbic acid are bound to the wallpaper. The stain resistance is not described at all, and since there is no layer having stain resistance on the surface of the wallpaper, it cannot be a wallpaper that has both deodorant and stain prevention functions. Moreover, the polyvinyl chloride resin hardly permeates odorous substances such as ammonia and hydrogen sulfide, and hinders the contact between the odorant and the deodorant. Therefore, as in Example 2 of the same Japanese Patent Laid-Open No.
It is necessary to make holes with a needle roll to increase the contact area, and it is unavoidable that the strength of the wallpaper decreases. JP 62-
No. 6984 and Japanese Patent Laid-Open No. 63-235518 describe a deodorant fiber in which an iron (II) -phthalocyanine derivative is supported on polyvinyl alcohol, but there is no description about wallpaper.

[0010]

DISCLOSURE OF THE INVENTION As described above, a laminated film having an antibacterial property which is inexpensive, capable of thermal lamination at low temperature and easy to emboss, or having a deodorant and stain preventing function, and the laminated film There is a strong demand for vinyl chloride wallpaper or veneer laminated with films.

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

[0012]

The above object is to provide a polyalcohol layer or a resin composition layer containing a polyalcohol having a barrier property and an antibacterial property or a deodorant and stain resistant property of a plasticizer for a polyvinyl chloride resin, Achieved by laminating a specific adhesive composition, and by providing a laminate in which the laminated film is laminated on at least one side of a substrate, in particular, a polyvinyl chloride resin layer containing a plasticizer, particularly an outermost layer. To be done.

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, etc., 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. Compounds obtained by reacting all the hydroxyl groups of polyols 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, A compound containing two or more of the above isocyanate groups in the functional groups of a polyester having an average molecular weight of 3,000 or less and having at least one dicarboxylic acid component selected from succinic acid, glutaric acid, adipic acid, azelaic acid and sebacic acid as a constituent component. You may use together the compound etc. which were made to react. (Hereinafter, these are abbreviated as CN).

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
If it is less than 0.01 parts by weight, the adhesive strength with the polyalcohol composition film may be insufficient, and if it exceeds 15 parts by weight, the obtained laminated film may be blocked during storage and the embossability is also deteriorated. In addition, it does not exhibit sufficient adhesive strength at a temperature of 120 ° C. or less during thermal lamination.

In the present invention, the method for blending the vinyl chloride copolymer composition is not particularly limited, and the vinyl chloride copolymer and the CN are directly blended, or the solution of the vinyl chloride copolymer is blended 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 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 impeding 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 preferably 0.5 to
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 polyalcohol layer or the polyalcohol composition layer and the polyvinyl chloride resin layer containing the plasticizer tends to be low.
If it exceeds 0 μm, the cost becomes high, which is not preferable.

In the present invention, a polyalcohol layer is used to provide a laminate in which the laminate film and a substrate, in particular, a polyvinyl chloride resin layer having a plasticizer are laminated on at least one surface, particularly on the outermost layer. It shows the barrier property and stain resistance of the plasticizer for polyvinyl chloride resin even after laminating and embossing the wallpaper.

In the present invention, the polyalcohol is a polyalcohol obtained by reducing a polyketone composed of a carbon monoxide-ethylene copolymer, and in particular, the repeating unit represented by the formula (I) is 80% or more. The polyalcohol containing is preferable from the viewpoint of gas barrier properties, mechanical properties, and moldability.
The content of the repeating unit is more preferably 90% or more, particularly preferably 95% or more, and most preferably 97% or more.

[0022]

Embedded image

The above polyketone is a carbon monoxide-ethylene type copolymer, and the carbon monoxide-ethylene type copolymer is obtained by copolymerizing carbon monoxide and ethylene, or Representative examples include those obtained by copolymerizing carbon oxide and ethylene as a main component with an unsaturated compound other than ethylene. Here, as the unsaturated compound other than ethylene, an olefin having 3 to 12 carbon atoms,
Examples thereof include dienes having 4 to 12 carbon atoms, vinyl esters, aliphatic unsaturated carboxylic acids, aliphatic unsaturated carboxylic acid salts, and aliphatic unsaturated carboxylic acid esters. Examples of the copolymer include a random copolymer and an alternating copolymer, and an alternating copolymer having a high carbonyl group content is preferable.

Examples of the olefin having 3 to 12 carbon atoms include propylene, butene-1, isobutene, pentene-
1,4-methylpentene-1, hexene-1, octene-1, dodecene-1, styrene and the like can be mentioned, but propylene, olefin having 4 to 8 carbon atoms, or propylene and olefin having 4 to 8 carbon atoms. A combination system with is preferred. Examples of the diene having 4 to 12 carbon atoms include butadiene, isoprene, 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl pivalate and the like. Also,
Examples of the aliphatic unsaturated carboxylic acid, its salt and its ester include acrylic acid, methacrylic acid, maleic anhydride,
Maleic acid, itaconic acid, acrylic acid ester, methacrylic acid ester, maleic acid monoester, maleic acid diester, fumaric acid monoester, fumaric acid diester, itaconic acid monoester, itaconic acid diester (as these esters, methyl ester, ethyl ester Alkyl ester such as ester), acrylate,
Examples thereof include maleic acid salts and itaconic acid salts (these salts include monovalent or divalent metal salts).

The polyketone can be produced by a known method, for example, US Pat. No. 2,495,286 and JP-A-53-128690, JP-A-53-128691.
JP-A-59-197427 and JP-A-61-912.
26, JP-A-62-232434, JP-A-62-5.
3332, JP-A-63-3025, JP-A-63-1
05031, JP-A-63-154737, JP-A-1
The methods described in JP-A-149829, JP-A-1-201333, JP-A-2-67319 and the like can be mentioned, but the method is not particularly limited thereto. Next, as a method for obtaining a polyalcohol by reducing the carbonyl group in the polyketone, a method of reducing a part or all of the carbonyl group in the polyketone with hydrogen, for example,
JP-A-1-149828, JP-A-2-232228
JP-A-5-339367, JP-A-6-49203
And a method of treating a part or all of the carbonyl group in the polyketone with a metal hydrogen compound to reduce the polycarbonyl, for example, the method described in JP-A-1-204929.

The intrinsic viscosity [η] of the polyol is 0.2 to
It is 5 dl / g, preferably 0.5 to 3 dl / g (value measured by Ostwald viscometer at 30 ° C. in a mixed solvent of 15% by weight of water-85% by weight of phenol).

The polyalcohol may be a composition of two or more kinds of polyalcohols having different repeating units of the formula (I) or different polymerization degrees, and boric acid, an antioxidant and a slip agent may be used as long as they do not interfere with the present invention. Agent, colorant, UV absorber,
A thermoplastic resin such as a lubricant or polyamide may be blended.

In the present invention, by using a resin composition in which a polyalcohol is mixed with a carboxylic acid-modified polyethylene resin (hereinafter abbreviated as CPE), adhesion between the composition layer and the vinyl chloride copolymer composition layer is achieved. Not only will the strength be improved, but embossing will be 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. Polyalcohol and C
The blending ratio of PE is 95 to 50% by weight of polyalcohol,
CPE 5 to 50% by weight, preferably polyalcohol 9
2 to 55% by weight and CPE 8 to 45% by weight. CPE
If the content is less than 5% by weight, the glossiness is not satisfied, and 50% by weight
If it exceeds the range, the plasticizer blocking property is poor, the film-forming property is deteriorated, and there are disadvantages such as the formation of holes in the film.

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 upon blending with a polyalcohol, and the effect of delustering the film is poor. If it exceeds 5 mol%, the viscosity during the blending operation is large and the film-forming property becomes 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 an 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 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 mono- or diester, itaconic acid mono- or diester and the like are mentioned, but maleic anhydride is preferred. Polyethylene resin refers to high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ethylene-based copolymers (ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, etc.)
However, high density polyethylene is preferable.

In the present invention, a typical example of the inorganic oxo acid salt having a specific antibacterial metal ion is a metal ion of the inorganic oxo acid salt exchanged with a metal ion having an antibacterial property. Here, examples of the inorganic oxo acid salt include silicates, phosphates, titanates, antimonates, and the like, and examples of the silicates include magnesium metasilicate aluminate, calcium silicate, magnesium silicate, and phosphorus. As the acid salt, calcium phosphate, zirconium phosphate, as the titanate, potassium titanate, calcium titanate, and as the antimonate, compounds such as sodium antimonate are preferable, and particularly magnesium metasilicate aluminate and calcium phosphate are mainly used. Apatite as a component is also preferable from the viewpoint of safety.
Apatite is also called apatite, and is a general term for fluorapatite, chlorapatite, and hydroxyapatite.

The oxo acid salt may be preformed or granular. The particle size is 2μm in order to develop the antibacterial property, especially the antibacterial property of wallpaper.
It is particularly preferable that the thickness be 0.5 μm or less.

As the metal ion having an antibacterial property to be ion-exchanged, a metal ion usually used as an antibacterial agent or a bactericide, for example, silver, copper, zinc, tin, mercury, lead, cadmium or the like can be applied. Especially, metal ions of silver, copper, zinc, and tin are desirable in terms of safety to human body.

These metal ions are ion-exchanged with the metal ions of the oxo acid salt by a conventional method.

For example, the ion exchange of silver, copper, zinc, tin, etc. is carried out in a region where the pH value is lower than the pH value for forming hydroxide and the oxo acid salt is not dissolved. That is, pH is 9 to 4 for silver, pH 6 to 4 for copper, and pH for zinc.
The temperature range is preferably in the range of 9 to 4 and 60 ° C. or higher. The proportion of the antibacterial metal ion to be ion-exchanged is appropriately 0.1 to 90 mol% of the ion-exchange capacity of the oxo acid salt, and the ion-exchanged ion in the antibacterial agent is the antibacterial agent. Is preferably 0.01 to 40% by weight. If the metal ion is less than the above-mentioned minimum value, the antibacterial property is not sufficient, and if it exceeds the maximum value, the metal ion becomes unstable and the antibacterial effect is not stable and long-lasting.

The antibacterial agent used in the present invention is different from silver zeolite (aluminosilicate hydrous alkali metal salt or alkaline earth metal salt ion exchanged with a metal ion such as silver). It is possible to use together with other antibacterial agents such as silver zeolite.

In the present invention, the deodorant is not particularly limited as long as it is a deodorant stable at the film forming temperature. Examples include iron (II) compound-organic acid compositions, tree liquor, silicates, activated carbon, iron (II) -phthalocyanine derivatives, etc., but activated carbon turns the film black,
The iron (II) -phthalocyanine derivative has a dark green film, which limits its use.
Organic acid compositions, tree sap and silicates are preferred. Iron (I
As the compound I), any compound can be used as long as it dissolves in water to form a divalent iron ion. Examples include iron (II) inorganic salts such as ferrous sulfate, ferrous nitrate, ferrous chloride, ferrous bromide, ferrous iodide, ferrous gallate, ferrous malate. Examples thereof include iron (II) organic salts such as ferrous fumarate, and ferrous sulfate and ferrous chloride are preferable. The organic acid is not particularly limited as long as it is soluble in water.Examples of ascorbic acid, isoascorbic acid, and ascorbic acids such as metal salts thereof, citric acid, isocitric acid, lactic acid, tartaric acid, Examples thereof include carboxylic acids such as malic acid, and L-ascorbic acid is preferred.

In the present invention, the iron (II) compound-organic acid composition must have both bound. This can be prepared by once mixing and dissolving both components and drying and powdering an aqueous solution by spray drying, freeze drying, or the like. Iron (I
The weight ratio of I) compound to organic acid is 1: 0.0.
The range of 1 to 1.0 is preferable, and more preferably 1: 0.
It is in the range of 02 to 0.80. When the organic acid component is ascorbic acid, the weight ratio of the iron (II) compound to the organic acid component is preferably in the range of 1: 0.02-0.30, more preferably 1: 0.02-. 0.13, particularly preferably 1: 0.05 to 0.13. In the present invention, two or more iron (II) compounds or two or more organic acids may be used in combination. Iron (I
In the compound I) -organic acid composition, it is preferable to add alum as a stabilizer of the deodorant function in an amount of 2 to 20% by weight based on the total amount of the iron (II) compound and the organic acid. The alum is not particularly limited, but potassium alum, ammonia alum, and sodium alum are preferable.

In the present invention, as a method of incorporating the antibacterial agent into the resin, a twin-screw extruder, a Brabender plastograph or the like is used to blend the resin in advance, or the resin is directly supplied to various molding machines. There is a method of molding while kneading with a molding machine, but once a high-concentration master pellet is prepared with an extruder, and 1/1 to 1/30
A method in which a product diluted to a certain extent is subjected to melt extrusion molding is preferable. When the antibacterial agent is contained in the resin, a metal soap such as sodium stearate, magnesium stearate or zinc stearate, and a dispersion aid such as ethylene bis fatty acid amide or polyethylene wax may be added. Further, the content of the antibacterial agent is 10 to 0.1% by weight, preferably 5 to 0.2% by weight, based on the composition. If the content of the antibacterial agent is less than 0.1% by weight, the antibacterial function is not sufficient, and if it exceeds 10% by weight, the film is likely to be scratched and cannot be put to practical use. In addition to antibacterial agents, antioxidants, ultraviolet absorbers, lubricants, various resins, and the like may be blended with these resins as long as the object of the present invention is not impaired.

In the present invention, the method of incorporating the deodorant into the resin is such that it is preliminarily blended with the resin using a twin-screw extruder, Brabender Plastograph or the like, or it is directly supplied to various molding machines. Although there is a method of molding while kneading with a molding machine, a method of once preparing high-concentration master pellets with an extruder and then melt-extruding the diluted product to about 1/10 is preferable. Further, the content of the deodorant, relative to the amount of resin in the layer containing the deodorant,
It is 1 to 40% by weight, preferably 3 to 20% by weight. If the amount of the deodorant is less than 1% by weight, the deodorant function is not sufficient, and if it exceeds 40% by weight, the strength of the film becomes weak and it cannot be put to practical use. In addition to deodorants, these resins may be mixed with antioxidants, UV absorbers, lubricants, various resins, etc.
It is free as long as it does not impair the object of the present invention.

In the present invention, polyalcohol and CPE
As a method for obtaining a resin composition consisting of, a twin screw extruder, a melt blending pelletization in advance using a Brabender Plastograph, etc., then a method of forming a film by a melt extrusion method such as T die method or inflation method, Alternatively, there is 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 thickness of the polyalcohol layer or the resin composition layer of polyalcohol and CPE is not particularly limited, but is preferably 10 to 30 μm, and 10 μm.
If it is less than m, pinholes are likely to occur in the film layer during embossing, and the barrier properties of the plasticizer for polyvinyl chloride resin deteriorate. 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 in which a film made of a resin composition of polyalcohol and CPE is coated 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 25
It is achieved by storing at a temperature of ~ 45 ° C for 16 hours or more.

In the present invention, the 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 based on 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,
Phthalate ester plasticizers such as didecyl phthalate, dinonyl phthalate, butyllauryl phthalate, dilauryl phthalate and butylbenzyl phthalate, tricresyl phosphate, tributyl phosphate, phosphate 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 heat 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, is easy to emboss, does not change the laminate strength even after long-term use, and maintains antibacterial properties or deodorant and stain prevention functions, making it very useful as a wallpaper or decorative board. Is.

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

[0048]

【Example】

Example 1 Polyalcohol obtained by reducing carbon monoxide-ethylene copolymer {Repeating unit represented by formula (I) 96%, other 4
%, And an intrinsic viscosity [η] 0.8 dl / g} 75% by weight and a maleic anhydride graft modified high density polyethylene resin 25% by weight, using a twin screw extruder.
The mixture was pelletized at 210 ° C., and a film of the resin composition having a thickness of 20 μm was obtained at 210 ° C. using a single screw extruder. The gloss of the obtained film (Murakami gloss meter, measured at an incident light angle of 75 °) is 21%.
And was good.

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, pressure-bonded with a hot embossing roll of 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 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 investigate the barrier property of the plasticizer for polyvinyl chloride resin, 6 cm × 6 c on the polyalcohol surface of the wallpaper
m of a 70 μm thick non-plasticized polyvinyl chloride film was adhered, a load of 3 kg was applied to the non-plasticized polyvinyl chloride film, and the mixture was allowed to stand at 70 ° C. for 7 days to obtain the weight of the non-plasticized polyvinyl chloride film. The change was examined, but no increase in weight was observed, no stickiness on the surface of the polyalcohol was observed, and the migration of the plasticizer was completely prevented.

The ambient temperature in the above test is so high as not to be experienced in daily life, and it is generally said that the ambient temperature 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 examine the stain prevention function, oily red ink (Mitsubishi Marker manufactured by Mitsubishi Pencil Co., Ltd.) and soy sauce (Kikkoman Dark mouth manufactured by Kikkoman Co., Ltd.) in a size of 2 cm × 2 cm were applied to the polyalcohol surface of the wallpaper. Was applied and wiped off with gauze to which benzine was added 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 Polyalcohol obtained by reducing carbon monoxide-ethylene copolymer {90% of repeating unit represented by formula (I), other 1
A resin composition consisting of 0%, an intrinsic viscosity [η] 1.2 dl / g} 70% by weight and a maleic anhydride graft-modified high density low density polyethylene resin 30% by weight was used and a twin screw extruder was used. Blend pelletization was carried out at 0 ° C., and a film of the resin composition having a thickness of 15 μm was obtained at 220 ° C. using a single screw extruder. The glossiness of the obtained film was as good as 25%. The following was carried out and tested according to Example 1. 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 a maleic anhydride graft-modified high-density polyethylene resin was not added and a film of polyalcohol alone was obtained. The following was carried out and tested according to Example 1. The results are shown in Table 2, and all the effects were good.

Example 5 3.2 g of silver nitrate and 5.7 g of copper sulfate were dissolved in 5 l of pure water to adjust the pH to 5. In this aqueous solution, magnesium aluminometasilicate (Al ↓ 2O ↓ 3 ・ MgO ・ 2SiO)
↓ 2.7H ↓ 2O, average particle size 0.02μm, moisture content 20
125% by weight) and again adjusting the pH to 5, 6
Stirred at 0 ° C. for 1 hour. Then, it was washed with 5 equivalents of warm water, dried at 100 ° C. for 4 hours, and further baked at 600 ° C. for 2 hours to obtain an antibacterial agent.

Next, a polyalcohol obtained by reducing a carbon monoxide-ethylene copolymer {comprising 96% of repeating units represented by the formula (I) and 4% of others, and having an intrinsic viscosity [η] 0.8d.
L / g} 74% by weight, carboxylic acid-modified high-density polyethylene to 25% by weight, and 1% by weight of the above antibacterial agent were blended and pelletized at 220 ° C. using a twin-screw extruder. The blended pellets were subjected to a single screw extruder at 220 ° C. to obtain a 15 μm thick antibacterial polyalcohol film. Using a gravure coater, the vinyl chloride copolymer used in Example 1 having a solid content of 20% by weight was coated on this film at a coating amount of 2 g / m 2 (based on solid content), and at 70 ° C. It was dried for 4 minutes.

On the other hand, 100 parts by weight of the paper, 100 parts by weight of polyvinyl chloride resin and 5 parts by weight of the filler were added to the flame-retardant paper for backing impregnated with 24 parts by weight of the guanidine sulfamate flame retardant.
0 parts by weight, plasticizer (di-2-ethylhexyl phthalate) 55 parts by weight, pigment 20 parts by weight, flame retardant 3 parts by weight, stabilizer 2 parts by weight, foaming agent 2 parts by weight, and binazine (organic arsenic antibacterial agent). ) After laminating 2 parts by weight of the formulation, the vinyl chloride was foamed to obtain a vinyl chloride wallpaper.

Align the adhesive surface coated on the polyalcohol film with the polyvinyl chloride resin surface laminated on the paper, and
It was pressed with a hot embossing roll at 30 ° C. and simultaneously embossed to obtain a wallpaper having both the desired antibacterial property and stain prevention function.

The antifouling function was perfect as shown in Table 3.

To investigate the antibacterial function, E. coli (Esc
herichia coli) 3.0 × 10 ↑ 4 /
The above-mentioned antibacterial EVO was added to 5 ml of physiological saline having a concentration of ml.
When 1 g of H film was added and shaken at 28 ° C. for 24 hours, the number of viable cells was measured, and as shown in Table 4, 1.0 × 10 ↑ 2 /
It was very good with ml. Separately, the antibacterial polyalcohol film was stored at 20 ° C. for half a year and the antibacterial function was examined.
It did not deteriorate over time and retained its antibacterial function for a long time.

Comparative Example 3 The procedure of Example 5 was repeated except that polyethylene was used instead of polyalcohol, and the antifouling function and the antibacterial function were tested in the same manner. The results are shown in Table 3 and Table 4, respectively.
As shown in, the stain prevention function was incomplete and the antibacterial function was also present, but it was inferior to the polyalcohol type.

Example 6 The same procedure as in Example 5 was carried out except that the carboxylic acid-modified high-density polyethylene was not used, and the antifouling function and the antibacterial function were similarly tested. The results are shown in Table 3,
As shown in Table 4, all the effects were good. Separately, the antibacterial polyalcohol film was stored at 20 ° C. for half a year, and the antibacterial performance was examined. As a result, the antibacterial function was maintained for a long time without deterioration with time.

Example 7 140 g of ferrous sulfate heptahydrate and 0.9 g of L-ascorbic acid were dissolved in 360 g of water, and 0.2 g of alum was further dissolved. This solution is sent at a flow rate of 40 ml / min,
Atomizing air amount 15m ↑ 3 / min, dry air amount 6m ↑ 3 / min,
Spray drying was performed under conditions of an inlet temperature of 120 ° C. and an outlet temperature of 75 ° C. to obtain a powdered iron (II) -ascorbic acid composition.

Next, a polyalcohol obtained by reducing a carbon monoxide-ethylene copolymer {90% of repeating units represented by the formula (I), other 10%, intrinsic viscosity [η] 1.2 dl /
g} of polyalcohol (95% by weight) and the above iron (II)-
5 wt% of the ascorbic acid composition was blended and pelletized at 220 ° C using a twin-screw extruder, and a film having a thickness of 15µ was obtained at 220 ° C using a single-screw extruder. Using a gravure coater, the film was coated with the vinyl chloride-based copolymer composition having a solid content of 20% by weight used in Example 1 so that the coating amount was 2 g / m 2 (based on solid content). It was dried at ℃ for 4 minutes.

On the other hand, 100 parts by weight of paper, 100 parts by weight of polyvinyl chloride resin, and 5 parts by weight of filler are added to flame-retardant paper for backing impregnated with 24 parts by weight of guanidine sulfamate flame retardant.
0 parts by weight, 55 parts by weight of plasticizer (di-2-ethylhexyl phthalate), 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 blowing agent are laminated, The vinyl chloride wallpaper was obtained by foaming the vinyl chloride.

The adhesive surface coated on the polyalcohol film and the polyvinyl chloride resin surface laminated on the paper are aligned, and 1
It was pressed with a hot embossing roll at 30 ° C. and simultaneously embossed to obtain a wallpaper having both the desired deodorant and stain prevention functions.

After standing for 2 days at room temperature, the adhesive strength of the above wallpaper was measured by T-type peeling, and it was found that the polyvinyl chloride layer was broken and had sufficient adhesive strength. The adhesive strength of the above-mentioned wallpaper was measured by T-type peeling after standing at room temperature for 50 days, but the polyvinyl chloride layer was destroyed and no decrease in adhesive strength due to the plasticizer was observed.

Further, as shown in Table 5, the blocking property of the plasticizer was such that the migration of the plasticizer was prevented completely.

The antifouling function was perfect as shown in Table 6.

In order to examine the deodorizing function, 2 cm of a 2 l polyethylene container was wetted with a 1% aqueous ammonia solution.
A filter paper with a size of × 2 cm and the wallpaper with a size of 10 cm × 10 cm were put in, and after 10 minutes, the odor intensity in the container was examined, but the odor was deodorized to a slight extent, As shown in Table 7, the deodorizing function was very excellent. In addition, the atmospheric concentration (ammonia concentration) in the above test is so high that it is not usually experienced in daily life, and maintaining efficacy even under these conditions means that it can withstand long-term use. .

Comparative Example 4 In Example 7, the acrylic copolymer containing 86 mol% of methyl methacrylate and 14 mol% of butyl methacrylate was used.
According to Example 7, except that a sheet obtained by thermally laminating a film having a thickness of 25 μ blended with the iron (II) -ascorbic acid composition and a vinyl chloride wallpaper was used, and finally performing a drilling operation with a needle roll. Then, the barrier property, antifouling function and deodorant function of the plasticizer were similarly tested. The results are shown in Table 5, Table 6 and Table 7, respectively, but the items other than the deodorizing function were not in a satisfactory state.

Example 8 In Example 7, first, a silicate (Daimseika Seikagyo Co., Ltd., Dime Shoe 3000) was used in place of the powdered iron (II) -ascorbic acid composition to modify maleic anhydride. 20 wt% of high-density polyethylene resin is blended and pelletized into a high-density polyethylene resin having a rate of 0.09 mol% and an MI of 1 g / 10 min, and 25 wt% of the high-density polyethylene resin is reduced to obtain a carbon monoxide-ethylene copolymer. Poly alcohol {(I)
A matte film comprising 96% of a repeating unit represented by the formula and 4% of others, and 75% by weight of a polyalcohol having an intrinsic viscosity [η] 0.8 dl / g} and having a surface glossiness of 20% on one side. Was carried out in the same manner as in Example 7, except that the barrier property of the plasticizer, the antifouling function, and the deodorizing function were tested in the same manner. The results are shown in Table 5, Table 6 and Table 7, respectively, and excellent results were obtained in all items.

Example 9 In Example 8, instead of the silicate, a tree liquid (available from
Kokonoe Super Clean WX-2041) was used, blend pelletization and film formation were carried out at 190 ° C, and the same procedure as in Example 8 was carried out except that a film having a thickness of 15 µm was used. The function and the deodorant function were similarly tested. The results are shown in Table 5, Table 6 and Table 7, respectively, and excellent results were obtained in all items.

Example 10 In Example 7, 100 parts by weight of polyvinyl chloride resin,
The procedure was carried out in the same manner as in Example 7 except that a vinyl chloride wallpaper laminated with a mixture of 50 parts by weight of a plasticizer, 60 parts by weight of a filler, and 3 parts by weight of a stabilizer was used. The odor function was also tested. The results are shown in Table 5, Table 6 and Table 7, respectively, and excellent results were obtained in all items.

[0081]

[Table 1]

[0082]

[Table 2]

[0083]

[Table 3]

[0084]

[Table 4]

[0085]

[Table 5]

[0086]

[Table 6]

[0087]

[Table 7]

[0088]

INDUSTRIAL APPLICABILITY The laminated film of the present invention can be heat-laminated at a low temperature and can be easily embossed. A wallpaper, a decorative board or the like laminated with the laminated film has an antibacterial property or a deodorant and stain preventing function. Can be maintained for a long time.

Claims (7)

[Claims] 1. A vinyl chloride component of 60 to 99 mol%, a vinyl acetate component and / or a carboxylic acid component of 1 to 40.
From a vinyl chloride-based copolymer composition layer comprising 100 parts by weight of a vinyl chloride-based copolymer containing 100% by mol and 0.1 to 15 parts by weight of a compound containing two or more isocyanate groups, and a carbon monoxide-ethylene-based copolymer A laminated film having a polyalcohol layer obtained by reducing the polyketone. 2. A vinyl chloride component of 60 to 99 mol%, a vinyl acetate component and / or a carboxylic acid component of 1 to 40.
From a vinyl chloride-based copolymer composition layer comprising 100 parts by weight of a vinyl chloride-based copolymer containing 100% by mol and 0.1 to 15 parts by weight of a compound containing two or more isocyanate groups, and a carbon monoxide-ethylene-based copolymer A laminated film having a resin composition layer comprising 95 to 50% by weight of a polyalcohol obtained by reducing the polyketone and 5 to 50% by weight of a carboxylic acid-modified polyethylene resin. 3. A vinyl chloride component of 60 to 99 mol%, a vinyl acetate component and / or a carboxylic acid component of 1 to 40.
From a vinyl chloride-based copolymer composition layer comprising 100 parts by weight of a vinyl chloride-based copolymer containing 100% by mol and 0.1 to 15 parts by weight of a compound containing two or more isocyanate groups, and a carbon monoxide-ethylene-based copolymer A laminated film having a resin composition layer comprising 90 to 99.9% by weight of a polyalcohol obtained by reducing the polyketone and 10 to 0.1% by weight of an inorganic oxo acid salt having an antibacterial metal ion. 4. A vinyl chloride component of 60 to 99 mol%, a vinyl acetate component and / or a carboxylic acid component of 1 to 40.
From a vinyl chloride-based copolymer composition layer comprising 100 parts by weight of a vinyl chloride-based copolymer containing 100% by mol and 0.1 to 15 parts by weight of a compound containing two or more isocyanate groups, and a carbon monoxide-ethylene-based copolymer Inorganic oxo acid salt having antibacterial metal ions in 90 to 99.9% by weight of a resin composition comprising 95 to 50% by weight of a polyalcohol obtained by reducing the polyketone of 5 to 50% by weight of a carboxylic acid-modified polyethylene resin A laminated film having a resin composition layer containing 10 to 0.1% by weight. 5. A vinyl chloride component of 60 to 99 mol%, a vinyl acetate component and / or a carboxylic acid component of 1 to 40.
From a vinyl chloride-based copolymer composition layer comprising 100 parts by weight of a vinyl chloride-based copolymer containing 100% by mol and 0.1 to 15 parts by weight of a compound containing two or more isocyanate groups, and a carbon monoxide-ethylene-based copolymer 99% to 60% by weight of polyalcohol obtained by reducing polyketone and deodorant 1
A laminated film having a resin composition layer consisting of -40% by weight. 6. A vinyl chloride component of 60 to 99 mol%, a vinyl acetate component and / or a carboxylic acid component of 1 to 40.
From a vinyl chloride-based copolymer composition layer comprising 100 parts by weight of a vinyl chloride-based copolymer containing 100% by mol and 0.1 to 15 parts by weight of a compound containing two or more isocyanate groups, and a carbon monoxide-ethylene-based copolymer A resin composition comprising 95 to 50% by weight of a polyalcohol obtained by reducing the polyketone and 5 to 50% by weight of a carboxylic acid-modified polyethylene resin and 99 to 60% by weight of a deodorant in the resin composition. Laminated film having layers. 7. The polyvinyl chloride copolymer composition layer side of the laminated film according to claim 1, claim 2, claim 3, claim 4, claim 5 or claim 6 containing a plasticizer. A wallpaper or decorative board laminated on at least one surface of a vinyl chloride resin layer.