JP2012201993A - Film for wallpaper and wall covering material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film for a wallpaper having a high antifouling property and high heat resistance and capable of exhibiting a deodorant effect in a short period of time, and to provide a wall covering material including the film for a wallpaper.SOLUTION: A film for a wallpaper comprises: 45 to 87 wt.% of a polypropylene resin; 10 to 50 wt.% of a polyethylene resin; and 3 to 15 wt.% of porous particles.

Description

The present invention relates to a film for wallpaper that is excellent in antifouling property and heat resistance and can exhibit a deodorizing effect in a short time. 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 this invention is to provide the film for wallpaper which is excellent in antifouling property and heat resistance, and can exhibit the deodorizing effect in a short time. 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 45 to 87% by weight of a polypropylene resin, 10 to 50% by weight of a polyethylene resin, and 3 to 15% by weight of porous particles. The present invention is described in detail below.

The inventor adds porous particles 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. It was investigated. As a result, the present inventor can obtain an antifouling layer excellent in deodorizing properties by adding porous particles, but depending on the type or amount of the resin and porous particles constituting the antifouling layer, It has been found that it takes time to remove the bad odor and the heat resistance is lowered.
In response to this problem, the present inventor uses a polypropylene resin and a polyethylene resin together as a resin constituting the antifouling layer, and the blending ratio of the polypropylene resin, the polyethylene resin and the porous particles is within a predetermined range. As a result, it was found that an antifouling layer excellent in antifouling property and heat resistance and capable of exhibiting a deodorizing effect in a short time was obtained, and the present invention was completed.

The film for wallpaper of the present invention has an antifouling layer.
The wallpaper film of the present invention may be a single-layer film having only an antifouling layer, or may be a film having two or more layers having an adhesive layer as described later in addition to the antifouling layer. Good.

The antifouling layer contains a polypropylene resin and a polyethylene resin.
The polypropylene resin is excellent in antifouling properties and heat resistance, has a low density, and has excellent malodor permeability. Therefore, by containing the polypropylene resin, the antifouling layer is excellent in antifouling properties, heat resistance and deodorizing properties.
Furthermore, since the 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 polyethylene resin has a low density and excellent odor permeability. Therefore, by containing the polyethylene resin, the antifouling layer has excellent deodorizing properties.
Further, when the resin constituting the antifouling layer is only the polypropylene resin, the antifouling layer is excellent in deodorizing properties, but it takes time to remove malodors. On the other hand, by containing the polypropylene resin and the polyethylene resin, the antifouling layer is not only excellent in deodorizing properties but also can exhibit a deodorizing effect in a short time. In addition, in this specification, being able to exhibit the deodorizing effect in a short time means that, for example, the deodorizing effect can be exhibited in about 1 to 8 hours, preferably in about 1 to 3 hours. .

In the present specification, the polypropylene-based resin means a polymer having a main component derived from propylene. In the present specification, the main component means a component that occupies 51% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more of the component.
The polypropylene resin is not particularly limited, and examples thereof include homopolypropylene resins and copolymers 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 polypropylene-based resins, a copolymer of propylene and one or more monomers copolymerizable with propylene is preferable, because it is superior in malodor permeability and improves the deodorizing property of the antifouling layer. A propylene-ethylene block copolymer is more preferred.

In the present specification, the polyethylene-based resin means a polymer whose main component is a component derived from ethylene. In the present specification, the main component means a component that occupies 51% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more of the component.
Although it does not specifically limit as said polyethylene-type resin, It is preferable that it does not have a polar group from the antifouling property of the said antifouling layer improving. Examples of the polar group include an ester group and an acetyl group, and examples of the polyethylene resin having such a polar group include an ethylene-vinyl acetate copolymer.
Specific examples of the polyethylene resin include, for example, low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), one or more monomers copolymerizable with ethylene, and ethylene. And a copolymer thereof. Examples of the monomer copolymerizable with ethylene include propylene, 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 polyethylene-based resins, low-density polyethylene (LDPE) is preferable because it is superior in odor permeability and the antifouling layer can exhibit a deodorizing effect in a shorter time.

The lower limit of the content of the polypropylene resin in the antifouling layer is 45% by weight and the upper limit is 87% by weight. When the content of the polypropylene resin is less than 45% by weight, the antifouling property of the wallpaper film is lowered or the dimensional stability is lowered due to a decrease in heat resistance. If the content of the polypropylene resin exceeds 87% by weight, the wallpaper film takes time to remove malodor. The preferable lower limit of the content of the polypropylene resin in the antifouling layer is 55% by weight, the preferable upper limit is 81% by weight, the more preferable lower limit is 60% by weight, and the more preferable upper limit is 76% by weight.

The content of the polyethylene resin in the antifouling layer has a lower limit of 10% by weight and an upper limit of 50% by weight. If the content of the polyethylene resin is less than 10% by weight, the wallpaper film takes time to remove malodor. When the content of the polyethylene resin is more than 50% by weight, the antifouling property of the wallpaper film is lowered, or the dimensional stability is lowered due to a decrease in heat resistance. The upper limit with preferable content of the said polyethylene-type resin in the said antifouling layer is 40 weight%, and a more preferable upper limit is 30 weight%.

The antifouling layer contains porous particles.
Since the porous particles have deodorizing properties, 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 in the polypropylene resin and the polyethylene resin is reduced to cause agglomeration, and the film cannot be formed or has a deodorizing property 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 particles are at least one selected from the group consisting of phosphates, silicates, metal oxides, and metal phthalocyanine complexes because of their particularly good dispersibility in the polypropylene resin and the polyethylene resin. It is preferable to contain, and it is more preferable to contain phosphate and / or silicate.
When using porous particles other than these, the dispersibility of the porous particles in the polypropylene resin and the polyethylene resin may be reduced to cause agglomeration. 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 of the polypropylene resin and the polyethylene resin is improved and the deodorizing property of the wallpaper film is improved.

Although it does not specifically limit as said silicate, For example, 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.

Although it does not specifically limit as said metal oxide, Since the dispersibility with respect to the said polypropylene resin and the said polyethylene resin improves, an alumina oxide, beryllium oxide, a silicon oxide, 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, since the dispersibility of the porous particles with respect to the polypropylene resin is good, an antifouling layer having a uniform deodorizing property can be obtained.
If the content of the porous particles is less than 3% by weight, the deodorizing property of the wallpaper film is lowered. When the content of the porous particles exceeds 15% by weight, the antifouling property of the wallpaper film is lowered, or the dimensional stability is lowered due to the reduced heat resistance. Moreover, when content of the said porous particle exceeds 15 weight%, it will take time for the wallpaper film to remove malodor. The preferable lower limit of the content of the porous particles in the antifouling layer is 4% by weight, the preferable upper limit is 12% by weight, the more preferable lower limit is 5% by weight, and the more preferable upper limit is 10% by 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 wallpaper film of the present invention may have an adhesive layer for adhering to the vinyl chloride wallpaper. The adhesive layer is formed on the surface opposite to the antifouling 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. In the case of forming a laminated film, after the resin or resin pellet constituting each layer is put into each extruder, the laminated sheet is formed by, for example, a feed block method, a multi-manifold method, or a method using these in combination. After forming and cooling and fixing with a take-off 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, the film for wallpaper which is excellent in antifouling property and heat resistance, and can exhibit the deodorizing effect in a short time 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) Polypropylene resin / propylene-ethylene block copolymer (b-PP) (manufactured by Mitsui Chemicals, Inc .: F707V, MFR = 6.5 g / 10 min, density 0.9 g / cm ³ , melting point 163 ° C.)
(2) Polyethylene 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.)
(3) Zeolite containing porous particles and silver (average particle size 2 μm)
・ Zirconium phosphate (average particle size 1μm)

Example 1
Using a twin-screw kneading extruder, 85% by weight of propylene-ethylene block copolymer (b-PP), 10% by weight of low density polyethylene (LDPE), porous particles (silver-containing zeolite, average particle diameter 2 μm) ) 5% by weight was melt-kneaded at 200 ° C., extruded into a strand, cooled and solidified, and then 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 to 4 and Comparative Examples 1 to 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) Antifouling property Soy sauce or crayons were applied to the antifouling layer of the obtained film for wallpaper by a method in accordance with the performance evaluation regulations for the antifouling products 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 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).

(2) Deodorizing effect 1 L of compressed air is sealed in a 2 L Tedlar bag under the conditions of a regulator exhaust pressure of 0.12 MPa, a flow meter of 2.0 L / min, and 30 seconds, and a methyl mercaptan solution having a methyl mercaptan concentration of 40 ppm is obtained. After the injection, the mixture was 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, and 20 μm in thickness was put into this Tedlar bag, and the concentration of methyl mercaptan was measured immediately after feeding the wallpaper film and after 3 hours. The removal rate (%) after 3 hours when the initial concentration was 100% was determined.

(3) Heat resistance (dimensional stability)
The obtained wallpaper film was cut into a size of 10 cm long × 10 cm wide and immersed in warm water at 80 ° C. for 5 minutes, and then the vertical and horizontal dimensions of the wallpaper film were measured. The vertical and horizontal dimensional change rates were calculated from the following formula (1), and the average value of the vertical and horizontal dimensional change rates was determined.
Dimensional change rate (%) = {(L1-L2) / L1} × 100 (1)
In Formula (1), L1 represents the dimension of the wallpaper film before being immersed in 80 ° C. warm water for 5 minutes, and L2 is the dimension of the wallpaper film after being immersed in 80 ° C. warm water for 5 minutes. In addition, the case where the average value of the vertical and horizontal dimensional change rates was 1.5% or less was rated as ◯, and the case where it exceeded 1.5% was marked as x.

ADVANTAGE OF THE INVENTION According to this invention, the film for wallpaper which is excellent in antifouling property and heat resistance, and can exhibit the deodorizing effect in a short time 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 45 to 87% by weight of a polypropylene resin, 10 to 50% by weight of a polyethylene resin, 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.