JP2003328278A - Laminate film for wallpaper and wallpaper - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a laminate film for wallpaper having an excellent deodorizing function, color fastness in a thermal process, stain resistance and embossment followingness and wallpaper having the deodorizing function and excellent flatting properties, etc. <P>SOLUTION: The laminate film for the wallpaper comprises 100 mass parts wt. of a thermoplastic resin and 0.1-10 mass parts wt. of a deodorant comprising an iron (II) compound and a polyaminocarboxylic acid-based compound as constituent components. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a wallpaper having a deodorant function, a laminate film for wallpaper and a layer composed of at least one laminate film for wallpaper on the outermost surface and having a good matteness and appearance. Regarding

[0002]

2. Description of the Related Art A wallpaper is a wallpaper that is attached to a wall or ceiling in a room to improve its appearance. Vinyl wallpaper, inorganic wallpaper, etc. are known. In particular, wallpaper made of vinyl chloride resin is used. Often. Wallpaper made of vinyl chloride resin is excellent in price and workability, but it is also easy to get discolored due to weathering, stains easily, and does not easily come off. In addition, since it contains a large amount of plasticizer, there is a problem that the plasticizer migrates and the surface is contaminated after many years of use. As a way to improve these,
For a wallpaper made of vinyl chloride resin, a method is known in which a resin layer for preventing stains is formed on the surface of the wallpaper. In this stain-proof wallpaper, a method of laminating a thermoplastic resin film to a compound layer mainly composed of vinyl chloride resin, coating the surface with an acrylic resin paint, a urethane resin paint, and a urethane acrylic resin paint, etc. Has been processed.

Conventionally, acrylic resin films, polyolefin resin films, polyester resin films and the like have been known as thermoplastic resin films used for preventing wallpaper from being stained, and in particular, light discoloration resistance, chemical resistance,
From the viewpoint of stain resistance, it is known that an acrylic resin film and a saponified ethylene-fatty acid vinyl copolymer (hereinafter sometimes referred to as EVOH) film are suitable.

[0004] As for the wallpaper, the better the matteness of the surface, the higher the sense of quality and the more the wallpaper tends to be preferred. Therefore, in the case of a wallpaper produced by laminating a laminate film on a base material for wallpaper, it is general to use a matte film as the laminating film. As a method for producing a wallpaper by laminating a film on a base material, heat lamination is often performed through an embossing roll with a textured surface, and the matteness of the wallpaper is the same as that of the laminating film itself. Determined by the graininess when laminating with the material.
When heat laminating a base material that does not have a particularly high impact resilience, such as foamed vinyl chloride resin, the base material tends to be compressed and deformed when the temperature during lamination is high, and the embossed texture tends to deteriorate. It has been known.

On the other hand, in recent years, problems such as sick house syndrome and hypersensitivity to chemical substances have become a problem. It is considered that these are caused by an adhesive agent used when applying wallpaper, a gaseous chemical substance derived from a treating agent used in the process of processing a building material, and the like. In addition, in the living environment, various odorous gases such as cigarette smoke and spoiled gas derived from microorganisms around water are generated. For this reason, the demand for wallpaper having a function of adjusting the living environment, such as a deodorizing function, has been greatly increased.

[0006] Conventionally, as an acrylic resin film used as a laminate film for wallpaper, Japanese Patent Laid-Open No. 6-7319
No. 9 discloses an acrylic resin film containing polyethylene glycol and having excellent embossing followability. Further, JP-A-5-310963 discloses an antibacterial acrylic resin film, and JP-A-10-306165 discloses a functional acrylic resin film such as an antibacterial antistatic acrylic resin film.

However, although the acrylic resin films described in JP-A-6-73199 and JP-A-10-306165 have improved embossing followability due to polyethylene glycol, the acrylic resin films have excellent heat resistance and film winding state. Further improvement of blocking resistance is required. On the other hand, although heat resistance and blocking resistance are improved by lowering the content of polyethylene glycol, improvement of emboss followability and improvement of matting property are desired. There is a demand for a film that simultaneously satisfies the properties, blocking resistance, and matting property.

Further, Japanese Patent Laid-Open No. 5-310963,
JP-A-6-73199 and JP-A-10-306
Although Japanese Patent No. 165 suggests a method of imparting functions such as weathering discoloration, chemical resistance, stain resistance, antibacterial property and antistatic property to wallpaper, it is completely unclear about a method of imparting a deodorant function. Not disclosed.

For this reason, it is necessary to reduce the trace gas components that are harmful to health and cause discomfort, for example, by dealing with the adhesive components released indoors during construction in sanitary facilities such as hospitals and indoor spaces such as houses. There is a need for a laminated film for wallpaper that can be used in certain interior and interior spaces.

On the other hand, various kinds of deodorants having a deodorizing function, such as a physical adsorption type, a chemical adsorption type, and a decomposition type, have been conventionally known. Of these, a physical adsorption type deodorant such as zeolite has a limit in sustaining the effect because of its adsorption / desorption mechanism.
Further, it is often difficult to obtain a sufficient effect of the chemical adsorption type deodorant due to decomposition and volatilization of the resin during heat processing.
JP-A-60-145143, JP-A-2-2112
Japanese Unexamined Patent Publication No. 40 discloses a decomposable deodorant having an excellent thermal stability, which is composed of an iron (II) compound and a polyaminocarboxylic acid.

However, JP-A-60-145143
Japanese Patent Laid-Open No. 211240/1990 discloses a specific method for adding a decomposing deodorant to a plastic film and its effect, a specific example of use as a laminated film for wallpaper, and a laminated film for wallpaper. There is no suggestion of a concrete method for obtaining a good emboss followability.

On the other hand, as an odor eliminating film for wallpaper, Japanese Patent Application Laid-Open No. 8-258229 discloses an odor eliminating EVOH film which can be heat laminated.

However, in the method of using the deodorant composed of an iron (II) compound and ascorbic acid described in JP-A-8-258229, since the iron (II) compound is not sufficiently stabilized, iron (II) ) There is a problem of causing discoloration or deterioration due to the compound. In particular, when it is used in a method for producing a wallpaper that involves heat processing such as heat melting and heat lamination, the EVOH film has a poor appearance due to discoloration and deterioration, resulting in a low industrial utility value.

[0014]

That is, conventionally, excellent heat resistance discoloration resistance, weather discoloration resistance, chemical resistance, stain resistance, and emboss followability required for a laminated film for wallpaper have hitherto been obtained. Laminated films for wallpaper having an odor function have not been found, and development of a technology that satisfies these at the same time is strongly desired.

In view of the above-mentioned conventional state of the art, an object of the present invention is to provide a wallpaper laminating film having at least one layer having a deodorant function, and a wallpaper produced by laminating the film having excellent mattness. Another object of the present invention is to provide a wallpaper having a layer composed of the film on the outermost surface.

[0016]

[Means for Solving the Problems] The present inventors have found that iron (II)
We investigated a laminate film for wallpaper that combines a deodorant containing a compound and a polyaminocarboxylic acid compound as a constituent component with a thermoplastic resin, and has a deodorant function and can suppress discoloration during processing. It was found that a film can be obtained, and that a wallpaper having at least one layer composed of this film on the outermost surface has excellent matting properties and an excellent deodorizing function, and has completed the present invention.

That is, the present invention can be specified by the matters described below. (1) A laminate film for wallpaper containing 0.1 to 10 parts by mass of a deodorant having an iron (II) compound and a polyaminocarboxylic acid compound as constituent components with respect to 100 parts by mass of a thermoplastic resin. (2) The laminated film for wallpaper according to (1), wherein the deodorant further contains an organic acid as a constituent component. (3) The laminated film for wallpaper according to (1) or (2), wherein the thermoplastic resin is an acrylic resin. (4) The laminate film for wallpaper according to any one of (1) to (3), wherein the polyaminocarboxylic acid compound is ethylenediaminetetraacetic acid or a salt thereof. (5) A wallpaper having at least one layer of the wallpaper laminate film according to any one of (1) to (4) on the outermost surface. (6) The wallpaper according to (5), which has at least one layer made of a base material composed of a vinyl chloride resin.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The laminate film for wallpaper and the wallpaper of the present invention will be described below.

The thermoplastic resin which can be used in the present invention is not particularly limited, but EVOH or acrylic resin is preferable from the viewpoint of weather resistance, stain resistance, chemical resistance, and matting property.

As EVOH, known EVOH can be used, but EVOH shown below is preferably used in the laminated film for wallpaper of the present invention. That is, the ethylene content is 20 to 65 mol%, preferably 25 to 60 mol%, and the degree of saponification of the fatty acid vinyl component is 90.
EVOH is suitably used in an amount of at least mol%, preferably at least 95 mol%. When the ethylene content is 20 mol% or more, the water resistance is excellent and the embossability is also good. When the ethylene content is 65 mol% or more, the oil resistance is excellent, and it becomes difficult for oily pollutants to permeate, and the pollution resistance is improved. Also, the degree of saponification of the fatty acid vinyl component is 90 mol%.
When it is set to the above, the oil resistance is excellent and it becomes difficult for oily contaminants to permeate, and the pollution resistance is improved.

Examples of the fatty acid vinyl used as the monomer constituting the EVOH include vinyl acetate, vinyl pivalate, vinyl benzoate and the like, with vinyl acetate being preferred. The EVOH used in the present invention may contain a monomer other than ethylene and fatty acid vinyl, for example, a monomer such as propylene and N-vinylpyrrolidone, as long as the object of the present invention is not impaired.

The EVOH used in the present invention is two or more kinds of EVO having different ethylene contents, saponification degrees and polymerization degrees.
The composition of H may be used, or a composition containing a thermoplastic polymer other than EVOH may be used as long as the object of the present invention is not impaired.

As the acrylic resin which can be used in the present invention, known ones can be mentioned. In the laminated film for wallpaper of the present invention, the acrylic resin composition (A) shown below is particularly used. preferable.

The acrylic resin composition (A) includes the thermoplastic polymers (A-1) and (A-3) constituting the acrylic resin composition (A) and the rubber-containing graft polymer (A-).
2) based on the total mass of the thermoplastic polymer (A-
1) 0 to 20% by mass, rubber-containing graft polymer (A-
2) 5 to 100% by mass, thermoplastic polymer (A-3) 0 to
It is an acrylic resin composition composed of 95 mass% (the sum of these is 100 mass%).

In the following, the thermoplastic polymer (A-1)
And (A-3) and the rubber-containing graft polymer (A
-2) will be described.

The thermoplastic polymer (A-1) which can be used in the present invention is 50 to 100% by mass of methyl methacrylate and 0 to 50 of at least one other vinyl monomer copolymerizable therewith. Mass% (thermoplastic polymer (A-1)
(The percentage of each monomer is shown based on the mass of all the monomers constituting the above).

The thermoplastic polymer (A-1) is a component that plays an important role in film moldability, and the reduced viscosity of the thermoplastic polymer (A-1) is important in relation to film moldability. is there. The thermoplastic polymer (A-1) has a reduced viscosity (polymer 0.1 g is dissolved in chloroform 100 ml,
Polymers having a (measured in ° C) of more than 0.1 L / g are preferred.
The reduced viscosity is more preferably more than 0.1 L / g and 2 L / g or less, further preferably 0.2 to 1.2.
L / g. When the reduced viscosity exceeds 0.1 L / g, a film having good thickness accuracy can be obtained.

Other vinyl monomers copolymerizable with methyl methacrylate that can form the thermoplastic polymer (A-1) include alkyl acrylates, methacrylic acid alkyl esters, aromatic vinyl compounds, A vinyl cyanide compound or the like can be used.

The production of the thermoplastic polymer (A-1) is preferably carried out by an emulsion polymerization method, and the powdery form of the thermoplastic polymer (A-1) is obtained by a known emulsion polymerization method and post-treatment method. be able to.

The rubber-containing graft polymer (A-2) has a function of imparting excellent impact resistance and elongation to the laminated film for wallpaper of the present invention, and has rubber elasticity containing an alkyl acrylate as a main component. An inner layer having a layer structure of one layer or two or more layers formed from a polymer having a compound (may be referred to as an elastic polymer), and one layer formed from a polymer containing an alkyl methacrylate as a main component. Two
It is a multi-layered graft polymer having an outer layer having a layer structure of one or more layers.

The rubber-containing graft polymer (A-2) is composed of 35 to 99.9% by mass of alkyl acrylate ester and other copolymerizable vinyl, based on the mass of all monomers constituting the elastic polymer. Layer structure of one layer or two or more layers formed by polymerizing a monomer composition comprising 0 to 64.9% by mass of a monomer and 0.1 to 10% by mass of a copolymerizable crosslinkable monomer In the presence of 100 parts by mass of the elastic polymer having the following formula, based on the mass of all the monomers constituting the polymer mainly composed of the methacrylic acid alkyl ester forming the outer layer,
50 to 100 mass% of methacrylic acid alkyl ester,
A monomer or monomer composition comprising 0 to 50% by mass of a vinyl-based monomer copolymerizable with this is usually added to the range of 10 to 2000.
At least 1 part by weight, preferably 20-200 parts by weight
It can be obtained by carrying out a graft polymerization in a step or more.

As the acrylic acid alkyl ester constituting the elastic polymer, those having an alkyl group having 1 to 8 carbon atoms are used, and among them, butyl acrylate and 2-ethylhexyl acrylate are preferable.

Other copolymerizable vinyl monomers that can form an elastic polymer are preferably methacrylic acid alkyl esters such as methyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate, styrene, and acrylonitrile.

The copolymerizable crosslinkable monomer constituting the elastic polymer is not particularly limited, but ethylene glycol dimethacrylate, butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate,
Triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diallyl maleate, trimethylolpropane triacrylate, allyl cinnamate and the like are preferable, and these can be used alone or in combination.

Specific examples of the methacrylic acid alkyl ester constituting the polymer having the methacrylic acid alkyl ester as the main component forming the outer layer include methyl methacrylate, ethyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate. , Cyclohexyl methacrylate and the like.

Further, the copolymerizable vinyl-based monomer that can form the polymer having the methacrylic acid alkyl ester as the main component forming the outer layer is not particularly limited, but specifically, acrylic acid is used. Examples thereof include alkyl acrylates such as methyl, butyl acrylate and cyclohexyl acrylate, styrene and acrylonitrile.

The rubber-containing graft polymer (A-2) used in the present invention can be obtained by known emulsion polymerization. A chain transfer agent and other polymerization aids may be used during the polymerization. Known chain transfer agents can be used, but mercaptans are preferable.

The thermoplastic polymer (A-3) which can be used in the present invention has 1 to 4 carbon atoms based on the mass of all the monomers constituting the thermoplastic polymer (A-3). Methacrylic acid alkyl ester having alkyl group (sometimes referred to as methacrylic acid alkyl ester) 50 to 9
It may be produced by polymerizing a monomer composition comprising 9% by mass, 1 to 50% by mass of alkyl acrylate, and 0 to 49% by mass of at least one other vinyl monomer copolymerizable therewith. it can.

Reduced viscosity of the thermoplastic polymer (A-3) (0.1 g of the polymer was dissolved in 100 ml of chloroform to obtain 25
0.01-0.1 L / g is preferable,
0.03-0.08 L / g is more preferable.

As the methacrylic acid alkyl ester constituting the thermoplastic polymer (A-3), methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like are preferable, and methyl methacrylate is more preferable.

As the acrylic acid alkyl ester constituting the thermoplastic polymer (A-3), methyl acrylate,
Ethyl acrylate, butyl acrylate and the like are preferable.

Further, as the other vinyl monomer capable of constituting the thermoplastic polymer (A-3), a known vinyl monomer, for example, an aromatic vinyl compound such as styrene,
Vinyl cyanide monomers such as acrylonitrile, unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, N-phenylmaleimide, N-cyclohexylmaleimide and the like can be used.

The method for producing the thermoplastic polymer (A-3) is as follows:
Although not particularly limited, it is possible to perform polymerization by a known method such as suspension polymerization, emulsion polymerization, bulk polymerization and the like. A chain transfer agent or other polymerization aid may be used during the polymerization. Known chain transfer agents can be used, but mercaptans are preferable.

The deodorant used in the present invention is a composition containing an iron (II) compound and a polyaminocarboxylic acid compound as essential components.

As the iron (II) compound, iron (II) sulfate,
Examples include iron (II) chloride, iron (II) nitrate, iron (II) bromide, iron (II) iodide, iron (II) gallate, iron (II) malate, and iron (II) fumarate. . The iron (II) compound is not particularly limited as long as it dissolves in water to form divalent iron ions.

The polyaminocarboxylic acid compound used in the present invention refers to an organic compound having an amine structure and two or more carboxyl groups in the molecule, and specific examples thereof include ethylenediaminetetraacetic acid and transcyclohexanediaminetetraacetic acid. Examples thereof include polyaminocarboxylic acids such as acetic acid, 1,2-diaminopropane tetraacetic acid, glycol ether diamine tetraacetic acid and diethylenetriamine pentaacetic acid, and water-soluble salts thereof. Of these, ethylenediaminetetraacetic acid sodium salt is preferable from the viewpoint of economy.

In the present invention, the content of the polyaminocarboxylic acid compound is preferably 0.0001 to 0.8 part by mass, more preferably 1 part by mass of iron (II) in the iron (II) compound. Is 0.0005 to 0.2 part by mass, more preferably 0.001 to 0.05 part by mass. Stability of the iron (II) compound in the deodorant when the polyaminocarboxylic acid compound is in the range of 0.0001 to 0.8 part by mass with respect to 1 part by mass of the iron (II) in the iron (II) compound (Discoloration resistance) and deodorant property are improved.

Further, the deodorant used in the present invention may further contain an organic acid. Organic acids that can be used in this case include carboxylic acids, oxyacids,
For example, citric acid, citric acid such as isocitric acid, lactic acid,
Aliphatic and aromatic carvone such as tartaric acid, malic acid, hydroxybutyric acid, monoethyl tartrate, monoethyl citrate, gluconic acid, ketogluconic acid, ascorbic acid, salicylic acid, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid and gallic acid. Examples thereof include acid compounds and water-soluble salts thereof. In addition to the above, oxocarboxylic acids and polycarboxylic acids such as maleic acid are also included. Like the polyaminocarboxylic acid compound, the organic acid or its water-soluble salt also has a function of stabilizing the iron (II) compound in the deodorant.

When the polyaminocarboxylic acid compound is used in combination with an organic acid or a water-soluble salt thereof to achieve a balance, the stability of the deodorant can be improved without impairing the deodorant function, and the laminate for wallpaper of the present invention. It is possible to further enhance the deodorizing function of the film and the wallpaper.

In the present invention, the amount of the organic acid or the water-soluble salt thereof is 0 based on 1 part by mass of the polyaminocarboxylic acid compound.
~ 100 parts by mass can be added. Preferably 1.
It is 3 to 10 parts by mass. When the content of the organic acid or the water-soluble salt thereof is 100 parts by mass or less, sufficient effects are obtained and it is economical.

Alum can be added to the deodorant used in the present invention. By adding alum, the deodorizing function can be stabilized and the function as a flameproofing agent can be imparted. Alum is preferably added in an amount of 0.02 to 10 parts by mass, more preferably 0.1 to 0.5 parts by mass with respect to 1 part by mass of iron (II) in the iron (II) compound. Is good. The alum that can be added is not particularly limited, but potassium alum, ammonium alum, sodium alum, and the like are preferable, and burned alum is particularly preferable.

The deodorant used in the present invention is iron (I
From the viewpoint of stabilizing the I) ion, it is preferable that the iron (II) ion in the iron (II) compound is chelated by the polyaminocarboxylic acid compound. Such a deodorant can be prepared by once mixing and dissolving both components, and powdering this by a spray drying method, a freeze drying method or the like. These may be used as a carrier by appropriately adding zeolite, clay mineral, activated carbon and the like.

As a specific example of a commercially available deodorant which can be used in the present invention, "Efnika P601" (trade name, manufactured by Nanjing Efnika Co., Ltd.) can be mentioned.

As the content of the deodorant, the thermoplastic resin 1
It is necessary to use it in the range of 0.1 to 10 parts by mass with respect to 00 parts by mass. From the viewpoint of deodorant property and plasticizing effect, it is necessary to be 0.1 part by mass or more, more preferably 1 part by mass or more. From the viewpoint of film formability and appearance, the amount is required to be 10 parts by mass or less, and more preferably 5 parts by mass or less. It is more preferably 3 parts by mass or less.

Conventionally, when the amount of plasticizer such as polyethylene glycol is increased to plasticize, there is a possibility that pellets during pellet drying or films after film formation may be easily blocked. When a plasticizer such as polyethylene glycol is used, the deodorant used in the present invention can be plasticized without increasing the amount of the plasticizer by adjusting the amounts of the deodorant and the plasticizer used. Was impossible to manufacture, because a wallpaper with better matte properties can be obtained,
Industrial utility value is significantly increased. Compared to the case where polyethylene glycol (molecular weight 20000) having a melting point of 61 to 65 ° C is used as a plasticizer, the melting point of ethylenediaminetetraacetic acid used as a deodorant is 200 ° C or higher, and the melting point of citric acid is around 140 ° C. , L-ascorbic acid has a melting point of 1
Since the temperature is around 90 ° C., for example, blocking does not pose a problem when pellets are dried at 40 to 90 ° C., which is a general acrylic resin drying temperature.

When an acrylic resin is used as the thermoplastic resin used in the present invention, it is preferable to use an inorganic matting agent or an organic cross-linking matting agent.

As such a matting agent, known inorganic or organic crosslinking matting agents can be used. Examples of the inorganic matting agent include fine particles of mica and fine particles of talc. As the organic cross-linking matting agent, resin fine particles having a cross-linking structure having an average particle diameter of 1 to 20 μm are generally used. The organic cross-linking matting agent is preferably an acrylic resin-based one from the viewpoint of transparency. For example, crosslinked beads made of polymethylmethacrylate having an average particle diameter of 1 to 20 μm can be used.

The blending amount of the inorganic matting agent or the organic cross-linking matting agent is preferably 1 part by mass or more, and more preferably 5 parts by mass or more with respect to 100 parts by mass of the acrylic resin from the viewpoint of matting property. From the viewpoint of physical properties such as film-forming properties, it is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less.

A plasticizer may be added to the thermoplastic resin used in the present invention. Known plasticizers can be used. From the viewpoints of plasticizing effect, film appearance and economy, polyalkylene glycol is preferable, and among them, polyethylene glycol is particularly preferable.

The amount of the plasticizer added is usually in the range of 0 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin, from the viewpoint of blocking property during drying of pellets and heat resistance of the film.

A resin containing 0.1 to 10 parts by mass of a deodorant and 100% by mass of a thermoplastic resin, which is a raw material resin of the laminated film for wallpaper of the present invention, and other additives if desired ( If the melt viscosity of the laminated film raw material resin for wallpaper (sometimes referred to as resin) at 180 ° C and a shear rate of 6.1 sec ^-1 is 35,000 Pa · s or less, sufficient matteness is obtained without adding a plasticizer. Express. It is preferable to add a plasticizer when the melt film viscosity of the raw material laminate film resin for wallpaper at 180 ° C. and a shear rate of 6.1 sec ⁻¹ is 35000 Pa · s or more.

The melt viscosity of the resin pellets as the raw material for the laminate film for wallpaper used in the present invention is 180 ° C. and the shearing rate is 6.1 sec from the viewpoint of good matting property during lamination and good mattness. ^-1 is preferably 35,000 Pa · s or less,
It is more preferably 30,000 Pa · s or less.

Further, according to the present invention, by adding the deodorant, not only the deodorizing function which is the original function but also a good effect on the plasticization can be obtained at the same time. Making the graininess good when laminating on a substrate by plasticization is one of the factors that make the matteness after lamination good. By using a deodorant, plasticization, that is, good matteness after lamination, the wallpaper of the present invention has a high-grade feeling and is industrially useful.

The thermoplastic resin used in the present invention is, if necessary, a known general compounding agent such as a stabilizer, a lubricant, a processing aid, an impact resistance aid, a foaming agent, a filling agent, and the like. Colorants,
It may contain an ultraviolet absorber, an antibacterial agent, a fungicide and the like.

As the method for producing the laminated film for wallpaper of the present invention, any method such as T-die method, melt extrusion method such as inflation method, calendar method and the like may be used, but the T-die method is preferable from the viewpoint of economy. .

The thickness of the laminated film for wallpaper of the present invention is not particularly limited, but is preferably 100 μm or less, more preferably 5 to 50 μm, and 10 to 20 μm.
Is more preferable. When the thickness is 100 μm or less, the film has appropriate rigidity, so that the laminating property and the secondary processability are improved. Further, it is economically advantageous in terms of mass per unit area. Furthermore, the film-forming property is stable and the laminate film for wallpaper can be easily manufactured.

The wallpaper of the present invention can be produced by laminating the wallpaper laminate film of the present invention on a substrate.

As the base material that can be used in the present invention, a base material composed of a known thermoplastic resin can be used. In the production of the wallpaper of the present invention, polyvinyl chloride, polypropylene, a film-like or sheet-like substrate composed of polyethylene terephthalate is processable,
It is preferably used from the viewpoint of price. The thickness of the base material is not particularly limited, but is generally 50 to 3000 μm, preferably 70 to 200 μm.

The method for producing the wallpaper of the present invention is not particularly limited, and a known laminating method can be adopted, but a thermal lamination method using an embossed heating roll is general.

For a base material such as paper or a base material composed of a thermosetting resin which is difficult to be heat-sealed, the laminate film for wallpaper of the present invention and the base material are interposed with an adhesive layer interposed. The wallpaper of the present invention can be laminated and formed.

In the wallpaper of the present invention, an intermediate layer may be provided between the laminate film for wallpaper of the present invention and the substrate, if necessary. Examples of the intermediate layer used as necessary include a printed layer, a plated layer, an adhesive layer, a colored resin layer, and the like.

The wallpaper of the present invention is excellent in deodorant property, weather resistance, chemical resistance, stain resistance and the like, and is particularly excellent in deodorant function. Therefore, the wallpaper is in contact with malodorous gas and health. It is possible to reduce the gas that may harm the odor and is suitable for use as wallpaper for indoor interiors, bathroom interiors, vehicle interiors, hospital interiors, etc. where odors are likely to stay .

[0073]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these. In the examples, "part" means "part by mass".

The evaluation methods used in the examples are as follows.

(1) Matting property According to ASTM-D523, a 60 degree surface glossiness was measured and evaluated using a gloss meter GM-26D (trade name) manufactured by Murakami Color Research Laboratory.

(2) Pellet Melt viscosity Laminated film raw material for wallpaper Using resin pellets,
Using a Capillograph (trade name) manufactured by Toyo Seiki Seisakusho, Ltd., the melt viscosity was measured under the conditions of 180 ° C. and a shear rate of 6.1 sec ⁻¹ .

(3) Pellet blocking property Laminated film raw material for wallpaper A resin pellet was dried in a dehumidifying dryer in air at 60 ° C. for 12 hours, and the blocking state of the pellet was evaluated by touch. ○: It does not reach the solidification level, which is a problem in the process. X: It is fused and solidified.

(4) Film-forming property The film-forming property was evaluated by visually observing the film-forming state during film formation.

(5) Reduced Viscosity, Intrinsic Viscosity The reduced viscosity and the intrinsic viscosity are those obtained by A
It measured using chloroform as a solvent using the VL-2C automatic viscometer (brand name). The reduced viscosity was measured at 25 ° C. by dissolving 0.1 g of the sample in 100 ml of chloroform.

(6) Film Coloring Property The film coloring property was evaluated by visually observing the coloring state of the film during film formation. ○: Almost no discoloration. Δ: Some discoloration occurred. X: Discoloration is noticeable.

(7) Deodorizing property Deodorizing property is as follows. Using 91L formaldehyde (trade name), a deodorant test was conducted and evaluated as follows.

The gas stock solution was placed in a 1000 ml screw cap glass bottle with an inner lid, left for 1 hour to evaporate, and then 500 cm ² of the obtained film test piece was placed through a small hole opened in the inner lid, and at predetermined time intervals. The internal gas was sampled from a small hole, and the formaldehyde concentration was measured using a detector tube. The average of three measured values was used as the measured value.

Reference Example 1 Iron (II) sulfate heptahydrate 140
Parts and 0.9 parts of disodium ethylenediaminetetraacetate were dissolved in 360 parts of water, and 2.8 parts of alum was further dissolved. This solution is sent at a flow rate of 40 ml / min, and the atomizing air volume is 1
5 m ³ / min, dry air amount 6 m ³ / min, inlet temperature 120 ° C,
Spray-dried under the condition of outlet temperature of 75 ° C to obtain powdered deodorant (S
-1) was obtained.

Reference Example 2 Iron (II) sulfate heptahydrate 140
Parts, 0.2 parts of disodium ethylenediaminetetraacetate and 0.8 parts of citric acid were dissolved in 360 parts of water, and 2.8 parts of alum was further dissolved. 40 ml of this solution
/ Min, spray air amount 15 m ³ / min, dry air amount 6 m 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 powder deodorant (S-2).

Reference Example 3 Iron (II) sulfate heptahydrate 140
Parts and 0.9 parts of L-ascorbic acid were dissolved in 360 parts of water, and 2.8 parts of alum was further dissolved. This solution was sent at a flow rate of 40 ml / min, spray air amount was 15 m ³ / min, dry air amount was 6 m ³ / min, inlet temperature was 120 ° C, outlet temperature was 75 ° C.
Spray-drying was performed under the conditions described above to obtain a powder deodorant (S-3).

Example 1 Production of Thermoplastic Polymer (A-1) A reactor was charged with 200 parts of ion-exchanged water purged with nitrogen, and 1 part of an emulsifier potassium oleate and 0.3 part of potassium persulfate were charged. . Subsequently, 40 parts of methyl methacrylate, 10 parts of n-butyl acrylate, and 0.0 of n-octyl mercaptan.
05 parts were charged and the polymerization was completed by stirring at 65 ° C. for 3 hours under a nitrogen atmosphere. Followed by methyl methacrylate 48
Part, and a monomer mixture consisting of 2 parts of n-butyl acrylate were added dropwise over 2 hours and maintained for 2 hours after completion of the addition to complete the polymerization. The obtained latex was added to a 0.25% sulfuric acid aqueous solution, the polymer was acid-deposited, then dehydrated, washed with water, and dried to obtain a powdery thermoplastic polymer (A-1). Reduced viscosity (ηsp / c) of the obtained thermoplastic polymer (A-1)
Was 0.38 L / g.

Production of Rubber-Containing Graft Polymer (A-2) The following (a) was charged into a reaction vessel and stirred, under a nitrogen atmosphere at 80 ° C. for 180 minutes, to obtain the monomer composition shown below. (B) was continuously added, and then polymerization was further performed for 120 minutes to obtain a latex of an elastic polymer.

In the presence of the latex of the elastic polymer,
Subsequently, (c) shown below was added, and the monomer composition (d) shown below was continuously added for 170 minutes at 80 ° C. under a nitrogen atmosphere while stirring, and then at 80 ° C. for 60 minutes. Polymerization was continuously performed for minutes to obtain a latex of the rubber-containing graft polymer (A-2).

Calcium acetate was added to the latex of the rubber-containing graft polymer (A-2) to coagulate, aggregate and solidify the latex, which was filtered, washed with water and dried.
A rubber-containing graft polymer (A-2) was obtained.

(A) Deionized water 310 parts Partially neutralized product of a mixture of sodium hydroxide containing 40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid and 60% di (polyoxyethylene nonylphenyl ether) phosphoric acid 0 0.5 part Sodium carbonate 0.05 part Sodium formaldehyde sulfoxylate 0.5 part Iron (II) sulfate heptahydrate 0.00004 part Ethylenediaminetetraacetic acid disodium 0.0002 part (b) Butyl acrylate 80.8 Parts Styrene 18.3 parts Allyl methacrylate 0.9 parts t-Butyl hydroperoxide 0.3 parts Mono (polyoxyethylene nonylphenyl ether) phosphoric acid 40% and di (polyoxyethylene nonylphenyl ether) phosphoric acid 60% Partially neutralized product of sodium hydroxide mixture 1.1 parts (c) Deionized water 1 0.0 parts Sodium formaldehyde sulfoxylate 0.12 parts (d) Methyl methacrylate 56.5 parts Butyl acrylate 3.0 parts n-Octyl mercaptan 0.16 parts t-Butyl hydroperoxide 0.09 parts Mono Partially neutralized product of a mixture of (polyoxyethylene nonylphenyl ether) phosphoric acid 40% and di (polyoxyethylene nonylphenyl ether) phosphoric acid 60% sodium hydroxide 0.4 part Thermoplastic polymer (A-3) As (A-3), the mass ratio of methyl methacrylate / methyl acrylate is 90/10, reduced viscosity (ηsp / c) =
A thermoplastic polymer of 0.051 L / g was used.

Production of laminated film for wallpaper and wallpaper Thermoplastic polymer (A-1) 2 obtained as described above
Parts, 50 parts of the rubber-containing graft polymer (A-2), 100 parts of the acrylic resin composition (A) consisting of 48 parts of the thermoplastic polymer (A-3), and 2 parts of the deodorant (S-1), Mica as an inorganic matting agent (“MICA M-40” manufactured by Repco Co., Ltd.)
OH ”; trade name) 8 parts, polyethylene glycol as a plasticizer (“ PEG20000 ”manufactured by Sanyo Kasei Co., Ltd .;
10 parts of the product name) and 2 parts of an antibacterial agent ("Bioside 3000D" manufactured by Taisho Technos Co., Ltd .; product name) were mixed with a Henschel mixer. Then, using a 40 mmφ screw type extruder (L / D = 26), the cylinder temperature was 200.
The mixture was melt-kneaded at ˜260 ° C. and a die temperature of 250 ° C. and pelletized. The obtained pellets were dried at 60 ° C. for 12 hours and then extrusion-molded using a T-die to obtain a wallpaper laminated film having a thickness of 15 μm.

The obtained laminated film for wallpaper was laminated on an embossed laminating roll at 150 ° C. and 3 MPa.
Under the conditions described above, thermal lamination was applied to a soft vinyl chloride resin film having a thickness of 100 μm to obtain a wallpaper. The evaluation results are shown in Table 1.

Example 2 A wallpaper was obtained in the same procedure as in Example 1 except that the amount of the deodorant (S-1) added was changed to 3.5 parts. The evaluation results are shown in Table 1.

Example 3 A wallpaper was obtained in the same procedure as in Example 1 except that the deodorant (S-1) in Example 1 was changed to the deodorant (S-2). The evaluation results are shown in Table 1.

(Example 4) In Example 1, the deodorant (S-1) was added to "Efnika P60" manufactured by Nanfang Efnika Co., Ltd.
A wallpaper was obtained by the same procedure as in Example 1 except that the wallpaper was changed to "1" (trade name). The evaluation results are shown in Table 1.

Example 5 A wallpaper was obtained in the same procedure as in Example 1 except that the addition amount of polyethylene glycol as a plasticizer was changed to 7.5 parts. The evaluation results are shown in Table 1. Due to the plasticizing effect of the deodorant, good matting properties could be obtained even if the polyethylene glycol of the plasticizer was reduced.

Example 6 EV having an ethylene content of 44 mol% and a saponification degree of a vinyl acetate component of 99.5 mol%
75 parts of OH (MI = 5.5 g / 10 minutes), maleic anhydride graft-modified high-density polyethylene resin (MI = 0.3
g / 10 minutes) 25 parts, and 2 parts of deodorant (S-1) are kneaded and pelletized at 210 ° C. using a twin screw extruder, and a T-die method at 210 ° C. using a single screw extruder. To obtain a 20 μm thick laminate film for wallpaper.

A resin composition comprising 100 parts by mass 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 mass of hexamethylene diisocyanate was added to give a solid content of 20 mass%. Was dissolved in a mixed solvent of methyl ethyl ketone: toluene = 1: 1 so that the above film was immediately coated on the film using a gravure coater, and dried at 70 ° C. for 4 minutes to obtain a laminated film. Coating amount of resin composition is 2 g / m ² (based on solid content)
Met. The laminated film was heat-laminated on a soft vinyl chloride resin film having a thickness of 100 μm under the conditions of 110 ° C. and 3 MPa using an embossing laminating roll to obtain a wallpaper. The evaluation results are shown in Table 1.

(Example 7) In Example 6, the deodorant (S-1) was added to "Efnika P60" manufactured by Nanfang Efnika Co., Ltd.
A wallpaper was obtained in the same procedure as in Example 6, except that the wallpaper was changed to 1 ”(trade name). The evaluation results are shown in Table 1.

Comparative Example 1 A wallpaper was obtained in the same procedure as in Example 1 except that the deodorant was not added. The evaluation results are shown in Table 1. This comparative example shows that an effective deodorizing function cannot be obtained without using a deodorant.

Comparative Example 2 A wallpaper was obtained in the same procedure as in Example 1 except that the addition amount of the deodorant (S-1) was changed to 15 parts in Example 1. The evaluation results are shown in Table 1. From this comparative example, it can be seen that the use of an excessive amount of deodorant deteriorates the film forming property.

(Comparative Example 3) A wallpaper was obtained in the same procedure as in Example 6 except that the deodorant was not added. The evaluation results are shown in Table 1. This comparative example shows that an effective deodorizing function cannot be obtained without using a deodorant.

Comparative Example 4 A wallpaper was obtained in the same procedure as in Comparative Example 1 except that the addition amount of polyethylene glycol as a plasticizer was changed to 15 parts in Comparative Example 1. The evaluation results are shown in Table 1. According to this comparative example, if polyethylene glycol alone is used to reduce the melt viscosity of the pellet, which is an index of gloss after lamination, the blocking property is severe and the film-forming property is deteriorated as compared with the case of using the deodorant together. I understand.

Comparative Example 5 A wallpaper was obtained in the same procedure as in Example 1 except that the deodorant (S-1) in Example 1 was changed to the deodorant (S-3). The evaluation results are shown in Table 1. From this comparative example, it can be seen that when iron (II) -ascorbic acid-based (S-3) is used as a deodorant, discoloration of the laminate film for wallpaper produced by heating in the production process is noticeable.

[0105]

[Table 1]

[0106]

The laminate film for wallpaper of the present invention comprises:
When it is laminated on a substrate by a laminating method, it has an excellent deodorizing function, and it is possible to obtain a wallpaper having good matteness and appearance.

The wallpaper laminate film of the present invention is used for producing a wallpaper having excellent deodorant properties, weather resistance, chemical resistance, stain resistance, etc., and the wallpaper of the present invention can prevent malodorous gas and health. It is suitably used as a wallpaper for indoor interiors, bathroom interiors, vehicle interiors, hospital interiors, etc., where gas, which may cause harm, easily accumulates, and has an extremely high industrial value.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/17 C08K 5/17 C08L 101/00 C08L 101/00 (72) Inventor Hideyuki Fujii Otake City, Hiroshima Prefecture Miyukicho No. 20-1 Mitsubishi Rayon Co., Ltd. Otake Office F-term (reference) 4F055 AA17 BA19 CA13 DA02 FA08 FA10 FA39 FA40 GA18 4F071 AA33 AB13 AB22 AB24 AC09 AC12 AF01 AH03 BB04 BB06 BB09 BC01 4F100 AA23A AA23H AC05H02 AH2HH02 AK15B AK25A AK25J AK46A AK46H AL04 AL05 AL09 AT00B BA02 BA03 BA04 BA05 BA10A BA10B CA30A GB08 JB01 JB16A JC00A JC00H JL06 JL09 JN26 YY00A YY00H 4J002 BG051 BN141 DD046 11736 DF026 DF026 DF036 DF026

Claims (6)

[Claims] 1. A laminate film for wallpaper, which contains 0.1 to 10 parts by mass of a deodorant having an iron (II) compound and a polyaminocarboxylic acid compound as constituent components with respect to 100 parts by mass of a thermoplastic resin. 2. The laminate film for wallpaper according to claim 1, wherein the deodorant further contains an organic acid as a constituent component. 3. The laminated film for wallpaper according to claim 1 or 2, wherein the thermoplastic resin is an acrylic resin. 4. The wallpaper laminate film according to claim 1, wherein the polyaminocarboxylic acid compound is ethylenediaminetetraacetic acid or a salt thereof. 5. A wallpaper having at least one layer, which is a laminate film for wallpaper according to any one of claims 1 to 4, on the outermost surface. 6. The wallpaper according to claim 5, which has a layer made of a substrate composed of at least one layer of vinyl chloride resin.