JP2012196811A - Film for wallpaper, and wall covering material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film for wallpaper that exhibits excellent porous dispersibility of porous particles, antifouling effect and deodorant effect even when manufactured by extrusion molding, and a wall covering material including the same.SOLUTION: This film for wallpaper includes an antifouling layer containing 85-97 wt.% of a polyolefin-based resin without having a polar group, and 3-15 wt.% of porous particles. In the film for wallpaper, the porous particle contains at least one selected from a group consisting of phosphate, silicate, metal oxide and a metal phthalocyanine complex.

Description

The present invention relates to a film for wallpaper having excellent dispersibility of porous particles even when produced by extrusion molding, and having excellent antifouling properties and deodorizing properties. 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 the vinyl chloride wallpaper is easily soiled, and that once it is soiled, it is difficult to remove the soil. 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 the present invention is to provide a wallpaper film having good dispersibility of porous particles and excellent antifouling properties and deodorizing properties even when produced 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 antifouling layer containing 85 to 97% by weight of a polyolefin-based resin having no polar group and 3 to 15% by weight of porous particles.
The present invention is described in detail below.

The inventor adds porous particles having deodorizing performance to an antifouling layer made of a resin having antifouling properties for the purpose of imparting both antifouling properties and deodorizing properties to wallpaper. It was investigated. However, from the viewpoint of productivity, it is preferable to produce the antifouling layer by extrusion, whereas in the case of extrusion, depending on the type or amount of the resin and porous particles constituting the antifouling layer, the porous particles As a result, the dispersibility was poor and aggregation occurred, resulting in problems that the film could not be formed or an antifouling layer having uniform deodorizing performance could not be obtained.
In response to this problem, the present inventor has a polyolefin resin in which the resin constituting the antifouling layer does not have a polar group, and the blending ratio of the polyolefin resin not having the polar group and the porous particles is predetermined. When it was within the range, it was found that the dispersibility of the porous particles with respect to the resin constituting the antifouling layer was good, and the antifouling layer could be produced satisfactorily by extrusion molding. The present inventors have found that a film for wallpaper having such an antifouling layer is excellent in antifouling properties and deodorizing properties, and has completed the present invention.

The film for wallpaper of the present invention has an antifouling layer.
The antifouling layer contains a polyolefin resin having no polar group. The polyolefin-based resin having no polar group is excellent in antifouling property, has a low density, and has excellent malodor permeability. Therefore, the antifouling layer is excellent in antifouling properties and deodorizing properties by containing the polyolefin resin having no polar group.
The wallpaper film of the present invention may be a single-layer film having only the antifouling layer, or a film having two or more layers having an adhesive layer as described later in addition to the antifouling layer. May be.

The polyolefin-based resin having no polar group may be any resin that is a polyolefin-based resin and does not have a polar group. For example, crystalline polypropylene-based resins and polyethylene-based resins are preferable. A polypropylene resin is more preferable. These polyolefin-based resins having no polar group may be used alone or in combination of two or more.
Since the crystalline polypropylene resin is excellent in embossing followability, the wallpaper film of the present invention can be firmly adhered even to the surface of the vinyl chloride layer of the foamed vinyl chloride wallpaper. . 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. For example, a homopolypropylene resin, a block copolymer of ethylene and propylene, a copolymer of propylene with one or more monomers copolymerizable with ethylene, etc. Is mentioned. When amorphous polypropylene is used, the antifouling property of the antifouling layer against oily dirt becomes insufficient.
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).

Examples of the polyethylene resin include low density polyethylene (LDPE), high density polyethylene (HDPE), and linear low density polyethylene (LLDPE).

The lower limit of the content of the polyolefin resin having no polar group in the antifouling layer is 85% by weight, and the upper limit is 97% by weight. When the content of the polyolefin resin not having the polar group is within the above range, the antifouling layer is formed by extrusion molding because the dispersibility of the porous particles in the polyolefin resin not having the polar group is good. Manufactured well.
When the content of the polyolefin resin having no polar group is less than 85% by weight, the antifouling property of the wallpaper film is lowered or the embossing followability is lowered. Moreover, when the content of the polyolefin resin having no polar group is less than 85% by weight, it becomes difficult to produce the antifouling layer satisfactorily by extrusion. If the content of the polyolefin resin having no polar group exceeds 97% by weight, the deodorizing property of the wallpaper film is lowered. The minimum with preferable content of the polyolefin-type resin which does not have the said polar group in the said pollution protection layer is 90 weight%, and a preferable upper limit is 95 weight%.

The antifouling layer contains porous particles.
Since the porous particles have a deodorizing performance, the antifouling layer is excellent in deodorizing properties by containing the porous particles.

The average particle diameter of the porous particles is not particularly limited, but a preferable lower limit is 0.5 μm and a preferable upper limit is 20 μm. When the average particle diameter is out of the above range, the dispersibility of the porous particles with respect to the polyolefin resin not having the polar group is deteriorated to cause agglomeration, and the film cannot be formed or has a deodorizing performance uniformly. An antifouling layer may not be obtained. The more preferable lower limit of the average particle diameter of the porous particles is 1 μm, and the more preferable upper limit is 10 μm.
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).

The porous particles may contain a metal, an organic compound, or the like inside.
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, a part or all of these metals can be contained in the porous particles by ion exchange with ammonium ions. Of these, zirconium, titanium, silver, copper or zinc is preferable.

The porous particle preferably contains at least one selected from the group consisting of phosphate, silicate, metal oxide and metal phthalocyanine complex, and contains phosphate and / or silicate. More preferably.
Since these porous particles have particularly good dispersibility with respect to the polyolefin-based resin having no polar group, when the porous particles are contained, the antifouling layer is particularly preferably produced by extrusion molding. . When porous particles other than these are used, the dispersibility of the porous particles in the polyolefin resin not having the polar group may be reduced to cause aggregation, resulting in failure to form a film or uniform deodorizing performance. In some cases, the antifouling layer may not be obtained.

Although it does not specifically limit as said phosphate, For example, zinc phosphate, aluminum phosphate, a zirconium phosphate etc. are mentioned. Among these, zirconium phosphate is preferable because dispersibility with respect to the polyolefin-based resin having no polar group is improved and deodorizing property of the wallpaper film is improved.

Although it does not specifically limit as said silicate, For example, a silica, a zeolite, etc. are mentioned. Especially, since the deodorizing property of the film for wallpaper improves, the silicate containing a metal in the inside is preferable, and the zeolite containing silver is more preferable. Moreover, as said silicate, the zeolite which contains a metal phthalocyanine complex in the inside is also preferable.

Although it does not specifically limit as said metal oxide, Since the dispersibility with respect to the polyolefin resin which does not have the said polar group improves, an alumina oxide, beryllium oxide, a silicon oxide, a zinc oxide, etc. are preferable. Of these, base-modified silicon oxide obtained by treating silicon dioxide with aqueous ammonia, ammonia gas, an aqueous alkali metal salt solution, an aqueous quaternary ammonium salt, an amine or the like is preferable.
Examples of the metal phthalocyanine complex include cobalt-phthalocyanine compounds and iron-phthalocyanine compounds.

The lower limit of the content of the porous particles in the antifouling layer is 3% by weight, and the upper limit is 15% by weight. When the content of the porous particles is within the above range, the antifouling layer is well manufactured by extrusion because the dispersibility of the porous particles in the polyolefin resin not having the polar group is good. The
If the content of the porous particles is less than 3% by weight, the deodorizing property of the wallpaper film is lowered. When content of the said porous particle exceeds 15 weight%, the antifouling property of the film for wallpaper will fall, or embossing followable | trackability will fall. On the other hand, if the content of the porous particles exceeds 15% by weight, it becomes difficult to produce the antifouling layer satisfactorily by extrusion. The minimum with preferable content of the said porous particle in the said antifouling layer is 5 weight%, and a preferable upper limit is 10 weight%.

The antifouling layer is a range that does not impair the characteristics of the wallpaper film of the present invention, such as flame retardants, antifungal agents, antibacterial agents, dampproofing agents, antistatic agents, antiblocking agents, lubricants, fillers, colorants, etc. An additive may be contained.
Moreover, although the said antifouling layer may be non-stretched or stretched, it is preferably non-stretched because the embossing followability is improved.

The thickness of the antifouling layer is not particularly limited, and is appropriately determined in consideration of the performance, price, etc. of the wallpaper film. The preferable lower limit is 1 μm, and the preferable upper limit is 100 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 100 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 film for wallpaper of the present invention may have an adhesive 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 antifouling layer may be warped, the design such as the design shown on the surface of the vinyl chloride layer of the vinyl chloride wallpaper may be concealed, The flexibility of the film may decrease.

As a method for producing the wallpaper film of the present invention, a method in which the antifouling layer is formed by an extrusion method, and then an adhesive solution is applied as necessary, followed by drying.
As a method of forming the antifouling layer by an extrusion method, for example, the resin constituting the antifouling layer and the porous particles are put into an extruder, extruded into a sheet form from a T die, and cooled and fixed by a take-up roll. After the conversion, a method of stretching uniaxially or biaxially as required can be used. When forming a laminated film, the resin or resin pellets that make up each layer are put into each extruder, and the laminated sheet is formed by, for example, a feed block method, a multi-manifold method, or a method using these in combination. Then, after cooling and fixing with a take-up roll, a method of stretching uniaxially or biaxially as required can be used.

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, even when manufactured by extrusion molding, the dispersibility of porous particles is good, and the film for wallpaper excellent in antifouling property and deodorizing property 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.

Resins and porous particles used in Examples and Comparative Examples are shown below.
(1) Resin used (1-1) Polyolefin-based resin / propylene-ethylene block copolymer (b-PP) having no polar group (Mitsui Chemical Co., Ltd .: F707V, MFR = 7.0, density 0.9 g / cm ³ , melting point 163 ° C.)
Low density polyethylene (LDPE) (manufactured by Nippon Polyethylene Co., Ltd .: Kernel KS430, MFR = 5.0, density 0.87 g / cm ³ , melting point 45 ° C.)
(1-2) Other Resins / Ethylene-Vinyl Acetate Copolymer (EVA) (Mitsui / DuPont Polychemical Co., Ltd .: Everflex V523, MFR = 14, Density 0.96 g / cm ³ , Melting Point 105 ° C.)

(2) Zeolite containing porous particles and silver (average particle size 2 μm)
・ Zirconium phosphate (average particle size 1μm)
・ Zirconium phosphate containing copper (average particle size 4μm)

Example 1
Using a twin-screw kneading extruder, 90% by weight of propylene-ethylene block copolymer (b-PP) and 10% by weight of porous particles (silver-containing zeolite, average particle diameter 2 μm) were melt-kneaded at 200 ° C. After extruding into a strand and cooling and solidifying, it was cut to obtain resin pellets. The obtained resin pellets are put into an extruder adjusted to 200 ° C. and extruded under conditions of a die temperature of 190 ° C., a cast roll temperature of 80 ° C., and a take-off speed of 7 m / min, and a 20 μm-thick wallpaper film is obtained. Obtained.

(Examples 2-6 and Comparative Examples 1-3)
A wallpaper film was obtained in the same manner as in Example 1 except that the types and blending amounts of the used resin and porous particles 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) Dispersibility of porous particles The antifouling layer of the film for wallpaper was visually observed. The case where almost no aggregation of the porous particles was observed was marked with ◯, the case where the dispersion state of the porous particles was not very good was marked with Δ, and the case where the dispersion was completely poor was marked with ×.

(2) Antifouling property Soy sauce or crayon was applied to the antifouling layer of the obtained wallpaper film by a method in accordance with the Japan Vinyl Industry Association's antifouling product performance evaluation regulations, and allowed to stand for 24 hours. The soy sauce was carefully wiped off with water, or the crayon was carefully wiped off with a detergent in the cloth, and the surface of the antifouling 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).

(3) Deodorizing effect 1 L of compressed air is sealed in a 2 L Tedlar bag under conditions of regulator exhaust pressure 0.12 MPa, flow meter 2.0 L / min, 30 seconds, ammonia solution 10 μL, trimethylamine solution 5 μL and methyl mercaptan solution 5 μL Were added so as to be 200 ppm of ammonia, 70 ppm of trimethylamine or 40 ppm of methyl mercaptan, respectively, and then allowed to stand 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 introduced into this Tedlar bag, and the concentration of ammonia, trimethylamine or methyl mercaptan was measured immediately after the introduction of the wallpaper film and after 24 hours. . The removal rate (%) after 24 hours when the initial concentration was 100% was determined.

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

Claims (3)

A film for wallpaper comprising an antifouling layer containing 85 to 97% by weight of a polyolefin-based resin having no polar group and 3 to 15% by weight of porous particles. The film for wallpaper according to claim 1, wherein the porous particles contain at least one selected from the group consisting of phosphates, silicates, metal oxides, and metal phthalocyanine complexes. A wall covering material comprising the wallpaper film according to claim 1 and a vinyl chloride wallpaper.