JP5636322B2 - Wallpaper film and wall covering - Google Patents

Description

The present invention relates to a film for wallpaper that is excellent in antifouling properties and deodorizing properties and is well manufactured by extrusion. The present invention also relates to a wall covering material having the wallpaper film.

As wallpaper used by being attached to indoor walls, closets, furniture, and the like, vinyl chloride wallpaper including a vinyl chloride layer is frequently used because of its excellent physical properties, good moldability and low cost. However, there is a problem that vinyl chloride wallpaper is easily soiled, and that once it is soiled, the soiling is difficult to remove. In addition, since the vinyl chloride wallpaper generally contains a plasticizer, the plasticizer bleeds on the surface, and there is a problem that dirt easily occurs due to adhesion of suspended matters in the air.

As a means of imparting antifouling properties to vinyl chloride wallpaper, a method of laminating and adhering an antifouling film having a base material layer made of a resin having antifouling properties to the surface of the vinyl chloride layer of vinyl chloride wallpaper It has been known. Conventionally, as such a base material layer, ethylene-vinyl acetate copolymer saponified product (EVOH) or an acrylic film has been used, and in particular, an EVOH film has been widely used. Further, for example, Patent Document 1 discloses an antifouling film using a transparent biaxially stretched polyester film as a base material layer, and Patent Document 2 uses a copolymerized polyester film as a base material layer. An antifouling film was disclosed.

On the other hand, as consumers become more conscious of their cleanliness, the wallpaper is required to have a deodorizing function for bad odors that give rise to unpleasant feelings such as body odors, food odors, pets, and garbage. In addition, the so-called sick house syndrome problem, in which a small amount of volatile organic compounds generated from building materials such as wallpaper affects the mucous membranes of the eyes, nose, throat, etc. of consumers, is also regarded as important.

In order to reduce such pollution in the living environment, wallpaper having excellent deodorizing properties has been developed.
For example, Patent Document 3 discloses a deodorizing wallpaper in which at least one of porous silicon dioxide supporting polyamine, hydrated zirconium oxide, zirconium oxide, hydrotalcite compound or hydrotalcite fired product is contained in the wallpaper. It is disclosed. In addition, for example, in Patent Document 4, in a wallpaper composed of a base material layer and a surface layer, a deodorant composed of a porous inorganic substance, an amine compound, and a metal oxide is provided on the upper side of the surface layer by a binder resin. Also disclosed is a deodorant wallpaper that is adhered together.

Japanese Patent Application Laid-Open No. 07-232415 JP 07-290667 A Japanese Patent Laid-Open No. 11-286899 JP 2006-348430 A

An object of this invention is to provide the film for wallpaper which is excellent in antifouling property and deodorizing property, and is manufactured favorably by extrusion molding. Another object of the present invention is to provide a wall covering material having the wallpaper film.

The present invention is a wallpaper film having an A layer on the surface side and a B layer on the wallpaper side, wherein the A layer contains a particulate adsorbent (I) and a crystalline polypropylene resin. The layer B contains a particulate adsorbent (II) and a crystalline polypropylene resin, and one of the particulate adsorbent (I) and the particulate adsorbent (II) is an amino acid. A particulate adsorbent carrying a compound having a group, and the other of the particulate adsorbent (I) and the particulate adsorbent (II) does not carry a compound having an amino group It is a film for wallpaper which is an agent.
The present invention is described in detail below.

The inventor adds a particulate adsorbent having deodorizing properties to an antifouling layer made of a resin having antifouling properties for the purpose of imparting both antifouling properties and deodorizing properties to wallpaper. I examined that. As a result, the present inventor has different types of malodor that can be removed depending on the type of particulate adsorbent. For example, in order to remove aldehyde-based malodor such as acetaldehyde, a compound having an amino group It has been found that a particulate adsorbent carrying no amino group is effective for removing bad odors such as ammonia, trimethylamine and methyl mercaptan.
However, from the viewpoint of productivity, it is preferable to produce an antifouling layer by extrusion molding, whereas one layer does not carry a particulate adsorbent carrying an amino group-containing compound and an amino group-containing compound. When both of the particulate adsorbents are added, a new problem arises that the film formation by extrusion cannot be performed satisfactorily because these particulate adsorbents influence each other.

In response to this problem, the present inventors laminated a B layer containing the particulate adsorbent and the crystalline polypropylene resin on the A layer on the surface side containing the particulate adsorbent and the crystalline polypropylene resin. Considered to do. The present inventor carries a particulate adsorbent carrying a compound having an amino group on one of the A layer and the B layer, and a compound having an amino group on the other of the A and B layers. By using a particulate adsorbent not found, it was found that a film for wallpaper having excellent antifouling properties and excellent deodorizing properties against a wide variety of bad odors can be produced by extrusion, and the present invention was completed. I came to let you.

The film for wallpaper of this invention has A layer used as the surface side, and B layer used as the wallpaper side.
The A layer contains a particulate adsorbent (I) and a crystalline polypropylene resin, and the B layer contains a particulate adsorbent (II) and a crystalline polypropylene resin.
Since the particulate adsorbent (I) and the particulate adsorbent (II) are deodorant, the A layer contains the particulate adsorbent (I), and the B layer is the particulate adsorbent. By containing the agent (II), both the A layer and the B layer can exhibit a deodorizing effect, and the wallpaper film of the present invention has excellent deodorizing properties.

Although it does not specifically limit as an average particle diameter of the said particulate adsorbent (I) and the said particulate adsorbent (II), A preferable minimum is 0.5 micrometer and a preferable upper limit is 20 micrometers. When the average particle diameter is out of the above range, the dispersibility of the particulate adsorbent (I) and the particulate adsorbent (II) with respect to the crystalline polypropylene resin may be reduced to cause agglomeration. It may not be possible, or a layer having a uniform deodorizing property may not be obtained. The minimum with a more preferable average particle diameter of the said particulate adsorbent (I) and the said particulate adsorbent (II) is 1 micrometer, and a more preferable upper limit is 10 micrometers.
In addition, in this specification, an average particle diameter means the mode particle diameter obtained from the particle size distribution measured using the laser diffraction type particle size distribution measuring apparatus (LA-500, Horiba, Ltd. make).

Although it does not specifically limit as a specific surface area of the said particulate adsorbent (I) and the said particulate adsorbent (II), A preferable minimum is 100 m < ² > / g and a preferable upper limit is 900 m < ² > / g. When the specific surface area is within this range, the particulate adsorbent (I) and the particulate adsorbent (II) can exhibit good deodorizing performance.

As the particulate particulate adsorbent constituting the particulate adsorbent (I) and the particulate adsorbent (II), the dispersibility with respect to the crystalline polypropylene resin is particularly good. , Preferably containing at least one selected from the group consisting of metal oxides and metal phthalocyanine complexes, and more preferably containing phosphates and / or silicates.
In the case of using a base particulate adsorbent other than these, the dispersibility of the particulate adsorbent (I) and the particulate adsorbent (II) with respect to the crystalline polypropylene resin may be reduced to cause aggregation. In some cases, the film cannot be formed or a layer having a uniform deodorizing property cannot be obtained.

In the present specification, the base particulate adsorbent means a particulate adsorbent serving as a base for the particulate adsorbent (I) and the particulate adsorbent (II). A particulate adsorbent (I) or a particulate adsorbent (II) can be obtained by supporting a compound having an amino group or a metal on the substrate particulate adsorbent. Further, the substrate particulate adsorbent may be used as it is as the particulate adsorbent (I) or the particulate adsorbent (II).

Although it does not specifically limit as said phosphate, For example, zinc phosphate, aluminum phosphate, a zirconium phosphate etc. are mentioned. Especially, since the dispersibility with respect to crystalline polypropylene resin improves and the deodorizing property of the said A layer and the said B layer improves, a zirconium phosphate is preferable.
Although it does not specifically limit as said silicate, For example, a zeolite etc. are mentioned.

Although it does not specifically limit as said metal oxide, Since the dispersibility with respect to the said crystalline polypropylene resin improves, an alumina oxide, beryllium oxide, a silicon oxide, a zinc oxide, etc. are preferable.
Examples of the metal phthalocyanine complex include cobalt-phthalocyanine compounds and iron-phthalocyanine compounds.

One of the particulate adsorbent (I) and the particulate adsorbent (II) is a particulate adsorbent carrying a compound having an amino group, and the other is a compound having an amino group. It is a particulate adsorbent that is not supported.
By containing such a particulate adsorbent, the A layer and the B layer are satisfactorily produced by extrusion. When one layer contains both a particulate adsorbent carrying a compound having an amino group and a particulate adsorbent not carrying a compound having an amino group, these particulate adsorbents influence each other. Therefore, the film formation by extrusion cannot be performed satisfactorily.
Further, the particulate adsorbent carrying an amino group-containing compound is particularly effective for removing aldehyde-based malodor such as acetaldehyde, and the particulate adsorbent not carrying an amino group-containing compound is particularly ammonia, It is effective for removing malodors such as trimethylamine and methyl mercaptan. By including particulate adsorbents having different types of malodors that can be removed in this manner, the wallpaper film of the present invention has excellent deodorizing properties against a wide variety of malodors.

In the present specification, the particulate adsorbent carrying (or not carrying) a compound having an amino group is a particle carrying (or not carrying) a compound having an amino group on the base particle adsorbent as described above. Means adsorbent.
The compound having an amino group is not particularly limited as long as it is a compound having one or more amino groups in the molecule, and examples thereof include aliphatic amines, aromatic amines, and alicyclic amines. Of these, compounds having one or more primary amino groups in the molecule are preferred.

The method for supporting the compound having an amino group on the substrate particulate adsorbent is not particularly limited. For example, a solution obtained by diluting the compound having an amino group with water or the like is mixed with the substrate particulate adsorbent. Then, a method for obtaining a particulate adsorbent that uniformly supports the compound having an amino group is mentioned. In such a method, since a compound having an excess amount of amino groups with respect to the base particulate adsorbent is usually used, it is washed with pure water after mixing and adheres to the surface of the obtained particulate adsorbent. After removing the compound having an excess amino group, drying is performed at 50 to 120 ° C.

As the particulate adsorbent carrying the compound having an amino group, for example, silicon oxide obtained by treating silicon oxide with the compound having an amino group is preferable.

The particulate adsorbent that does not carry a compound having an amino group may carry a metal inside the particulate adsorbent.
The metal is not particularly limited, and examples of the metal ion include alkali metal ions such as lithium ion, sodium ion and potassium ion, alkaline earth metal ions such as magnesium ion, calcium ion, strontium ion and barium ion. Can be mentioned. Examples of the metal include iron, silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium, zirconium, titanium, tin, cerium, and hafnium. For example, the metal can be supported on the base particulate adsorbent by ion exchange with ammonium ions. Of these, zirconium, titanium, silver, copper or zinc is preferable.

Examples of the particulate adsorbent that does not support the compound having an amino group and supports a metal include, for example, zirconium phosphate supporting silver or copper, zeolite supporting silver, zeolite supporting a metal phthalocyanine complex, and the like. Is mentioned.

The preferable lower limit of the content of the particulate adsorbent (I) or the particulate adsorbent (II) in the A layer or the B layer is 3% by weight, and the preferable upper limit is 15% by weight. If the content of the particulate adsorbent (I) or the particulate adsorbent (II) is less than 3% by weight, the deodorizing property of the A layer or the B layer may be lowered. When the content of the particulate adsorbent (I) or the particulate adsorbent (II) exceeds 15% by weight, the antifouling property of the A layer is reduced, or the embossing tracking of the A layer or the B layer is followed. May deteriorate. Moreover, when content of the said particulate adsorbent (I) or the said particulate adsorbent (II) exceeds 15 weight%, the said A layer or the said B layer may not be manufactured favorably by extrusion molding. The more preferable lower limit of the content of the particulate adsorbent (I) or the particulate adsorbent (II) in the A layer or the B layer is 5% by weight, and the more preferable upper limit is 10% by weight.

Since the crystalline polypropylene resin is excellent in antifouling property, the A film on the surface side contains the crystalline polypropylene resin, so that the wallpaper film of the present invention has excellent antifouling property. Become. The crystalline polypropylene resin has a low density and excellent malodor permeability, so that the A layer and the B layer have excellent deodorizing properties. Furthermore, since the crystalline polypropylene resin has a melting point suitable for extrusion molding, the A layer and the B layer are favorably produced by extrusion molding.

In addition, since the crystalline polypropylene resin is excellent in embossing followability, the wallpaper film of the present invention is firmly adhered even to the surface of the vinyl chloride layer of the foamed vinyl chloride wallpaper. Can do. In the present specification, the embossing follow-up property means that the wallpaper film follows the unevenness or the like that is the design of the wallpaper. When a film for wallpaper that does not have embossing followability is adhered to the surface of the wallpaper, the color may appear white or the surface irregularities may not be sharp.

The crystalline polypropylene resin is not particularly limited, and examples thereof include a homopolypropylene resin and a copolymer of propylene with one or more monomers copolymerizable with propylene. Examples of the monomer copolymerizable with propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene and 4-methyl. -1-pentene and the like can be mentioned. Among these crystalline polypropylene-based resins, since they are excellent in malodor permeability and the deodorizing properties of the A layer and the B layer are improved, the copolymer of propylene and one or more monomers copolymerizable with propylene is improved. A polymer is preferable, and a propylene-ethylene block copolymer is more preferable. In addition, when an amorphous polypropylene is used, the antifouling property with respect to the oily stain | pollution | contamination of the said A layer becomes inadequate.
In the present specification, “crystallinity” means that a clear melting point peak is observed when a raw material pellet or film is subjected to differential scanning calorimetry (DSC).

Said A layer and said B layer may contain other resin other than the said crystalline polypropylene resin in the range which does not inhibit the characteristic of the film for wallpaper of this invention.
It does not specifically limit as said other resin, For example, a polyethylene-type resin etc. are mentioned. Examples of the polyethylene resin include polyethylene resins having no polar group, such as low density polyethylene (LDPE), high density polyethylene (HDPE), and linear low density polyethylene (LLDPE), and ethylene-vinyl acetate copolymers. Examples thereof include polyethylene resins having a polar group such as (EVA).
Among the polyethylene resins, when used in the A layer, a polyethylene resin having no polar group is preferable so that the antifouling property of the A layer is not impaired. Low density polyethylene (LDPE) is more preferable because it can exhibit an odor effect.

When said A layer or said B layer contains the said polyethylene-type resin, the minimum with preferable content of the said polyethylene-type resin in the said A layer or the said B layer is 10 weight%, and a preferable upper limit is 50 weight%. When the content of the polyethylene resin is less than 10% by weight, the wallpaper film may take time to remove malodor. When the content of the polyethylene resin exceeds 50% by weight, the antifouling property of the wallpaper film may be lowered or the heat resistance may be lowered.

The A layer and the B layer are flame retardants, antifungal agents, antibacterial agents, dampproofing agents, antistatic agents, antiblocking agents, lubricants, fillers, coloring, as long as they do not impair the properties of the film for wallpaper of the present invention. An additive such as an agent may be contained.

The thicknesses of the A layer and the B layer are not particularly limited, and are appropriately determined in consideration of the performance, price, etc. of the wallpaper film. The preferable lower limit of each thickness is 1 μm, and the preferable upper limit is 50 μm. . If the thickness is less than 1 μm, the wallpaper film may be easily damaged by an external impact and may not be able to exhibit sufficient antifouling properties. If the thickness exceeds 50 μm, the manufacturing cost will rise, and the design such as the design shown on the surface of the vinyl chloride layer of the vinyl chloride wallpaper will be hidden, or the flexibility of the wallpaper film will be reduced. Sometimes.

The wallpaper film of the present invention may have another layer on the B layer in order to more firmly bond the adhesive layer described later and the B layer. Such other layers are also referred to as C layers in the present specification.
The C layer preferably contains a crystalline polypropylene resin as described above, similarly to the A layer and the B layer. Further, the C layer may contain other resins than the crystalline polypropylene-based resin in the same manner as the A layer and the B layer as long as the adhesiveness to the adhesive layer described later is not affected. Further, surface treatment such as corona treatment may be performed.

Although it does not specifically limit as thickness of the said C layer, A preferable minimum is 0.5 micrometer and a preferable upper limit is 20 micrometers. If the thickness is out of the above range, the wallpaper film may have reduced adhesion to the surface of the vinyl chloride layer of the vinyl chloride wallpaper.

The wallpaper film of the present invention may have an adhesive layer for adhering to the surface of the vinyl chloride layer of the vinyl chloride wallpaper on the surface opposite to the A layer.
The adhesive layer preferably contains a polyester polyol-acrylic copolymer and an isocyanate. The polyester polyol-acrylic copolymer plays a role of ensuring adhesion to the vinyl chloride layer of the vinyl chloride wallpaper. Examples of the polyester polyol-acrylic copolymer include those produced using a known polyester polyol compound and an acryloyl group-containing hydroxy compound as main raw materials.

Although it does not specifically limit as content of the said polyester polyol-acrylic copolymer in the said contact bonding layer, A preferable minimum is 10 weight% and a preferable upper limit is 95 weight%. When the content of the polyester polyol-acrylic copolymer is less than 10% by weight, strong adhesion to the surface of the vinyl chloride layer of the vinyl chloride wallpaper may not be obtained. When the content of the polyester polyol-acrylic copolymer exceeds 95% by weight, the antiblocking property of the adhesive layer may be lowered.
The minimum with more preferable content of the said polyester polyol-acrylic copolymer in the said contact bonding layer is 30 weight%, and a more preferable upper limit is 60 weight%.

The isocyanate functions as a crosslinking agent for crosslinking the polyester polyol-acrylic copolymer. As said isocyanate, the well-known organic isocyanate used when manufacturing a urethane resin is mentioned, for example. The isocyanate is preferably a blocked isocyanate blocked with a blocking agent that activates the isocyanate by heating.
The blocking agent is not particularly limited. For example, oxime systems such as acetone oxime and methyl ethyl ketone oxime; amide systems such as ε-caprolactam; active methylene systems such as dimethyl malonate and methyl acetoacetate; 3,5-dimethylpyrazole And the like. In addition, blocking agents such as phenols, alcohols, imidazoles, and ureas can also be used. These blocking agents may be used alone or in combination of two or more.

The isocyanate content in the adhesive layer is not particularly limited, but when the isocyanate has an NCO content of 12%, the polyester polyol-acrylic copolymer (solid content 100%) is 100 parts by weight. On the other hand, the preferred lower limit is 0.5 parts by weight, the preferred upper limit is 30 parts by weight, the more preferred lower limit is 5 parts by weight, and the more preferred upper limit is 20 parts by weight. When the isocyanate content is less than 0.5 parts by weight, the softening point of the polyester polyol-acrylic copolymer does not decrease and the crosslinking is not sufficient. In some cases, strong adhesiveness at low temperatures cannot be obtained. When the content of the isocyanate exceeds 30 parts by weight, the amount of the isocyanate is excessively increased, the softening point becomes close to room temperature, and it becomes a pressure-sensitive adhesive, which may increase the blocking.

The polyester polyol compound, the acryloyl group-containing hydroxy compound and the isocyanate may be those commercially available as a single substance, or those commercially available as a copolymer in a combination of two or more. May be used.

The adhesive layer may further contain additives such as an antistatic agent, an antiblocking agent, a lubricant, a filler, a colorant, etc., as long as the properties as the adhesive layer are not impaired. Depending on the case, other resins may be contained.
As said other resin, the binary copolymer which consists of monomers, such as polyethylene, ethylene, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, a ternary copolymer, etc. are mentioned, for example.

Although it does not specifically limit as thickness of the said contact bonding layer, A preferable minimum is 0.1 micrometer and a preferable upper limit is 20 micrometers. When the thickness is less than 0.1 μm, the adhesive force of the wallpaper film to the surface of the vinyl chloride layer of the vinyl chloride wallpaper may be insufficient, and the adhesive force tends to vary. If the thickness exceeds 20 μm, the manufacturing cost will increase, the wallpaper film will be warped, the design such as the design shown on the surface of the vinyl chloride layer of the vinyl chloride wallpaper will be concealed, the wallpaper film The flexibility may be reduced.

As a method for producing the wallpaper film of the present invention, the A layer, the B layer and, if necessary, the C layer are simultaneously formed by a coextrusion method, and then an adhesive liquid is applied as necessary. A method of drying is preferred. For example, when co-extrusion with a T-die is used, examples of the lamination method include a feed block method, a multi-manifold method, and a method using these in combination.
As a method of simultaneously molding the A layer, the B layer and, if necessary, the C layer by a coextrusion method, for example, a resin or resin pellet constituting each layer is put into an extruder, and a sheet is formed by a multilayer die. After extruding to refrigeration and cooling and fixing with a take-off roll, a method of stretching uniaxially or biaxially as required can be used.
Examples of the method for producing the resin pellets constituting each of the layers include a method of kneading the particulate adsorbent (I) or the particulate adsorbent (II) into the crystalline polypropylene resin to obtain a resin pellet. Is mentioned.

A wall covering material can be obtained by laminating a vinyl chloride wallpaper on the wallpaper film of the present invention. Such a wall covering is also one aspect of the present invention.

As a vinyl chloride layer of the said vinyl chloride wallpaper, what is used for a well-known vinyl chloride wallpaper can be mentioned, A foam or a non-foam may be sufficient. In particular, in the wall covering material of the present invention, even a vinyl chloride wallpaper containing a high-boiling plasticizer can be suitably used, so that the types of wallpaper that can be used are greatly expanded.
The vinyl chloride layer may be foamed after laminating the wallpaper film of the present invention. In addition, when printing on the said vinyl chloride layer, printing ink may be used normally. For example, those obtained by mixing and dissolving colorants such as pigments and dyes, dispersants, solvents and the like in acrylic, ethylene-vinyl acetate, urethane, and cellulose resins. The printing can be performed by a known method.

When producing the wall covering material of the present invention, the method for adhering the wallpaper film of the present invention to the surface of the vinyl chloride layer is not particularly limited, but it is preferable to adhere by the thermocompression bonding method. Since the thermocompression bonding method does not use organic solvents, solve the problems caused by organic solvents, such as impacts on the natural environment, fire hazards, health effects on workers and waste of resources. Can do.

In addition, the treatment conditions for adhering the wallpaper film of the present invention to the surface of the vinyl chloride layer by the thermocompression bonding method are not particularly limited, and are appropriately determined depending on the material constituting the adhesive layer, the composition thereof, and the like. . Moreover, when embossing is performed on the vinyl chloride wallpaper, the embossing may be performed simultaneously with the thermocompression bonding of the wallpaper film of the present invention and the vinyl chloride layer, or may be performed in a later step.

ADVANTAGE OF THE INVENTION According to this invention, the film for wallpaper which is excellent in antifouling property and deodorizing property, and is manufactured favorably by extrusion molding can be provided. Moreover, according to this invention, the wall covering material which has this film for wallpaper can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

The particulate adsorbents and resins used in the examples and comparative examples are shown below.
(1) Particulate adsorbent (1-1) Particulate adsorbent / silver-carrying zeolite (average particle diameter 2 μm) not supporting a compound having an amino group
・ Zirconium phosphate (average particle size 1μm)
・ Copper-supported zirconium phosphate (average particle size 4μm)
(1-2) Particulate adsorbent and amine compound-containing silica carrying an amino group-containing compound (average particle size 8 μm)

(2) Resin used (2-1) Crystalline polypropylene resin / propylene-ethylene block copolymer (b-PP) (Mitsui Chemical Co., Ltd .: F707V, MFR = 7.0 g / 10 min, density 0.9 g / cm ³ , melting point 163 ° C.)
(2-2) Other resin / low density polyethylene (LDPE) (manufactured by Nippon Polyethylene Co., Ltd .: Kernel KS430, MFR = 5.0 g / 10 min, density 0.87 g / cm ³ , melting point 45 ° C.)
・ Ethylene-vinyl acetate copolymer (EVA) (Mitsui / DuPont Polychemical Co., Ltd .: Everflex V523, MFR = 14 g / 10 min, density 0.96 g / cm ³ , melting point 105 ° C.)
-Talc-containing propylene homopolymer (manufactured by Takehara Chemical Co., Ltd .: MAX6070TAL, MFR = 1.0 g / 10 min, density 1.67 g / cm ³ )

Example 1
(Manufacture of layer A resin pellets)
Using a twin-screw kneading extruder, 90% by weight of propylene-ethylene block copolymer (b-PP) and 10% by weight of particulate adsorbent (I) (silver-supported zeolite, average particle diameter 2 μm) at 200 ° C. After melt-kneading, extrusion into a strand shape, cooling and solidification, cutting was performed to obtain a resin pellet for A layer.

(Manufacture of resin pellets for layer B)
Using a twin-screw kneading extruder, propylene-ethylene block copolymer (b-PP) 56% by weight, ethylene-vinyl acetate copolymer (EVA) 20% by weight, talc-containing propylene homopolymer 14% by weight and particles Adsorbent (II) (Amine compound-containing silica, average particle size 8 μm) 10% by weight is melt-kneaded at 200 ° C., extruded into a strand, cooled and solidified, then cut to obtain a B-layer resin pellet. It was.

(Manufacture of film for wallpaper)
Propylene-ethylene block copolymer (b-PP) as the resin for the A layer, the resin pellet for the B layer, and the resin for the C layer thus obtained was put into each extruder, and the extrusion temperature was 190 ° C. Co-extrusion is carried out under the conditions of a multilayer T die temperature of 190 ° C., a cast roll temperature of 60 ° C. and a take-off speed of 20 m / min, and has a three-layer structure of A layer (7 μm) / B layer (13 μm) / C layer (5 μm). A film having a thickness of 25 μm was obtained.
Polyisocyanate (Nippon Polyurethane), which is a block isocyanate, in a solution in which 30 parts by weight of a copolymer of polyester polyol and acrylic (manufactured by Nippon Polyurethane Industry Co., Ltd .: SH538A (solid content 40%)) is dissolved in 30 parts by weight of methyl ethyl ketone. Kogyo Co., Ltd .: Coronate 2507) 2 parts by weight was added and uniformly dispersed at room temperature to prepare an adhesive solution. The obtained adhesive liquid was applied on the C layer of the film obtained above so that the thickness after drying was 2 μm, and then dried to obtain a wallpaper film.

(Examples 2-7 and Comparative Examples 1-2)
A wallpaper film was obtained in the same manner as in Example 1 except that the type and blending amount of the resin and particulate adsorbent used were changed as shown in Table 1.

<Evaluation>
The following evaluation was performed about the film for wallpaper obtained by the Example and the comparative example. The results are shown in Table 1.

(1) When a film having a three-layer structure is obtained by melt extrusion coextrusion, ○ is indicated when film formation is possible regardless of the extrusion temperature, and Δ is indicated when film formation is possible by adjusting the extrusion temperature. The case where film formation was not possible irrespective of temperature was set as x.

(2) Dispersibility of particulate adsorbent The A layer and the B layer of the film for wallpaper were visually observed. The case where the aggregation of the particulate adsorbent was hardly observed was marked with ◯, the case where the dispersion state of the particulate adsorbent was not very good was marked with Δ, and the case where the dispersion was completely poor was marked with ×.

(3) Antifouling property Soy sauce or crayon was applied to the A layer of the obtained film for wallpaper by a method in accordance with the antifouling product performance evaluation regulations of the Japan Vinyl Industry Association and left for 24 hours. Subsequently, the cloth was soaked in water and the soy sauce was carefully wiped off, or the cloth was soaked in detergent and the crayon was carefully wiped off, and the surface of the A layer was visually evaluated according to the following criteria.
A five-step evaluation was performed with 5 being the most excellent antifouling property (a state in which almost no dirt was observable) and 1 being the most inferior in the antifouling property (a state where no dirt was wiped off).

(4) Deodorizing effect 1 L of compressed air is sealed in a 2 L Tedlar bag under the conditions of regulator exhaust pressure 0.12 MPa, flow meter 2.0 L / min, 30 seconds, ammonia solution 10 μL, trimethylamine solution 5 μL, methyl mercaptan solution 5 μL Then, 5 μL of the acetaldehyde solution was added so as to be 200 ppm of ammonia, 70 ppm of trimethylamine, 40 ppm of methyl mercaptan, or 30 ppm of acetaldehyde, respectively, and left at room temperature for 1.5 hours or more. Next, a wallpaper film cut into a size of 10 cm in length × 10 cm in width × 32 μm in thickness was put into this Tedlar bag. Immediately after the wallpaper film was put in and after 24 hours, ammonia, trimethylamine, methyl mercaptan, or acetaldehyde. Concentration was measured. The removal rate (%) after 24 hours when the initial concentration was 100% was determined.

ADVANTAGE OF THE INVENTION According to this invention, the film for wallpaper which is excellent in antifouling property and deodorizing property, and is manufactured favorably by extrusion molding can be provided. Moreover, according to this invention, the wall covering material which has this film for wallpaper can be provided.

Claims (5)

A wallpaper film having an A layer on the front side and a B layer on the wallpaper side,
The layer A contains a particulate adsorbent (I) and a crystalline polypropylene resin,
The B layer contains a particulate adsorbent (II) and a crystalline polypropylene resin,
One of the particulate adsorbent (I) and the particulate adsorbent (II) is a particulate adsorbent carrying a compound having an amino group, and the particulate adsorbent (I) And the other of the particulate adsorbents (II) is a particulate adsorbent that does not carry a compound having an amino group. The particulate particulate adsorbent constituting the particulate adsorbent (I) and the particulate adsorbent (II) is at least one selected from the group consisting of phosphates, silicates, metal oxides, and metal phthalocyanine complexes. The wallpaper film according to claim 1, further comprising: The content of the particulate adsorbent (I) in the A layer is 3 to 15% by weight, and the content of the particulate adsorbent (II) in the B layer is 3 to 15% by weight. The film for wallpaper according to 1 or 2. 4. The wallpaper film according to claim 1, wherein the A layer and the B layer further contain 10 to 50% by weight of a polyethylene resin. A wall covering material comprising the wallpaper film according to claim 1, and a vinyl chloride wallpaper.