JP2004300648A - Functional wallpaper - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce a functional wall paper controlling relative humidity in a space autonomously by the adsorption/desorption of water vapor of an inorganic porous body, also having the functions of adsorption and removal of hazardous chemical substances and bad smells in daily life, and antibacterial and antifungal functions. <P>SOLUTION: This functional wall paper is characterized by forming a humidity absorption/release layer consisting of a dried material of a composition containing an inorganic porous material having ≥0.1 mL/g volume of fine pores having 4-14 nm pore diameter measured by nitrogen gas adsorption and ≤1.5 mL/g total volume of the pores of 1-200 nm pore diameter and an organic material emulsion having (-)5-(-)50°C glass transition temperature on the surface of a substrate having flexibility, wherein, the composition is characterized by blending 200-400 pts. wt. inorganic porous material based on 100 pts. wt. dried weight of the organic emulsion. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention is a functional wallpaper having a function of autonomously controlling the relative humidity of a space by absorbing and desorbing water vapor to an inorganic porous body, and having a function of adsorbing and removing harmful chemicals and unpleasant odors, and an antibacterial and antifungal function. About.

  In recent years, the comfort of living environment has been increasing due to the improvement of heat insulation and the enhancement of heating equipment.However, in the case of artificial environment control using heat insulators and heaters, internal dew condensation occurs outside heat insulators. In addition, rot fungi and the like multiply and deteriorate the strength of the wall material, and as a result, it may not be possible to maintain sufficient strength against the earthquake. In addition, allergic problems associated with the propagation of mites and molds have also occurred. Furthermore, energy consumption will increase in the future, and it is necessary to reduce the load on the air conditioning equipment not only in terms of cost but also global environmental problems.

Artificial environmental control using the above-mentioned heat insulating materials and heaters is intended to perform temperature control in order to comfortably enjoy Japanese environmental conditions of high temperature, high humidity, or low temperature and low humidity. Environment can be realized. For this reason, humidity-control building materials have been developed that allow the interior material itself to have a function of absorbing and releasing moisture and adjust the humidity of the room without the need for air conditioning equipment or power. In recent years, urgent action has been taken to address the problem of indoor environmental pollution caused by harmful chemical substances resulting in sick house syndrome, and requests for deodorization and deodorization of unpleasant odors such as toilet odors, garbage odors, and pet odors. Is very strong.
Therefore, the above-mentioned humidity control building materials are expected to have not only humidity control properties but also effects of absorbing and removing harmful chemical substances and unpleasant odors in indoor air.

In recent years, many board- and tile-shaped building materials have been developed as humidifying materials, including diatomaceous earth-coated walls, which have been handed down since long ago. Building materials using calcium silicate (for example, see Patent Document 1), building materials using diatomaceous earth (for example, see Patent Document 2), building materials using zeolite (for example, see Patent Document 3), building materials using allophane ( For example, Patent Document 4) is described.
Further, as a sheet-shaped member, a sheet using a highly absorbent polymer substance (for example, see Patent Documents 5 and 6) and a sheet using diatomaceous earth (for example, see Patent Document 7) are disclosed.
JP-A-5-293267 JP-A-4-354514 JP-A-3-93632 Japanese Patent No. 3041348 JP-A-62-231740 JP-A-10-128892 JP-A-11-207853

  In addition, although the above-mentioned board-shaped and tile-shaped members have high moisture absorption / desorption capacity based on their thickness, they also have poor workability and are expensive, and therefore have the same performance. It is desired to develop a sheet-like member that has a shape and is suitable for reforming.

By the way, the moisture absorption action of the inorganic porous material is performed by the adsorption of water vapor to the pores. Liquefaction by gas condensation in the pores and gasification of the liquid occur depending on the pore diameter, and the pore radius at which such a state change occurs is called the Kelvin radius based on Kelvin's capillary aggregation theory. Is determined by the following Kelvin equation.
lnP / P0 = -2γV1 / rmRT
As is clear from the Kelvin equation, the position of humidity at which the amount of adsorption increases is determined by the size of the pore diameter.
Since the range of the relative humidity considered to be comfortable in the living environment is about 40 to 70%, the Kelvin radius of the pore is about 2 to 7 nm, that is If the hole diameter is 4 to 14 nm, it is possible to autonomously control the humidity within the range of the relative humidity that is most ideally comfortable.

However, the building materials described in Patent Literatures 1 to 4 are all tile-shaped and board-shaped, and as described above, there is a problem that the workability is poor.
In addition, since there is a limit to the moisture absorption capacity per unit volume, it is necessary to thicken the humidity control function layer in order to comfortably adjust the indoor air environment, and as described above, from the viewpoint of indoor workability and weight It is not necessarily a form suitable for use in an indoor environment, and there is a problem that it is necessarily expensive.

  The sheets using the superabsorbent polymer described in Patent Literatures 5 and 6 have problems such as the inability to completely release the once absorbed water, swelling due to water absorption, and easy occurrence of mold.

In the sheet using the inorganic moisture absorbing / releasing material described in Patent Document 7, since an emulsion having a high glass transition temperature is used, the flexibility and workability as wallpaper are not always sufficient.

In order to solve the above-mentioned problems, in the present invention, the volume of pores having a pore diameter of 4 to 14 nm measured by nitrogen gas adsorption is 0.1 ml / g or more on the surface of a flexible substrate. And a dried product of a composition containing an inorganic porous material having a pore diameter of 1 to 200 nm and a total pore volume of 1.5 ml / g or less, and an organic emulsion having a glass transition temperature of -5 to -50 ° C. A functional wallpaper on which a moisture release layer is formed, wherein the composition comprises 200 to 400 parts by weight of an inorganic porous material with respect to 100 parts by weight of a dry weight of the organic emulsion. Provide wallpaper.
This makes it possible to autonomously adjust the relative humidity of a space such as a living environment to a comfortable level of about 40 to 70%, and to produce a functional wallpaper having both flexibility and good appearance. . Here, having flexibility means that it does not break even when bent at 180 °. From the viewpoint of flexibility, the glass transition temperature of the organic resin in the emulsion is more preferably −30 ° C. or lower.

If the volume of the pores having a pore diameter of 4 to 14 nm is 0.1 ml / g or less, sufficient performance cannot be exhibited to adjust the relative humidity of the space comfortably and autonomously, and the total pore volume is 1%. When the concentration is more than 0.5 ml / g, the water contained in the organic emulsion is filled into the pores, so that it becomes difficult to use it as a coating composition. The more preferable range of the volume of the pore having a pore diameter of 4 to 14 nm is 0.3 ml / g or more.
Further, even when the water content is adjusted to obtain a preferable viscosity as the coating composition, if the total pore volume is 1.5 ml / g or more, a large amount of water is required, so that a large amount of heating energy is required during drying. This necessitates a substantial production difficulty and causes a problem that cracks easily occur in the moisture absorbing / releasing layer when a large amount of moisture is dried. Here, a more preferable range of the total pore volume is 1.0 mg / l or less.

Alternatively, in order to solve the above problem, in the present invention, the volume of pores having a pore diameter of 4 to 14 nm measured by nitrogen gas adsorption is 0.3 ml / g or more on the surface of a flexible substrate. And an inorganic porous material having a total pore volume of 1.8 ml / g or less having a pore diameter of 1 to 200 nm, a non-porous filler, and an organic emulsion having a glass transition temperature of -5 to -50C. A functional wallpaper on which a moisture absorbing / releasing layer made of a dried product of the composition is formed, wherein the composition contains 30 to 300 parts by weight of an inorganic porous material with respect to 100 parts by weight of a dry weight of the organic emulsion. A functional wallpaper, wherein 30 to 300 parts by weight of a porous filler is blended, and the total of the inorganic porous material and the non-porous filler is 100 to 600 parts by weight.
This makes it possible to autonomously adjust the relative humidity of a space such as a living environment to a comfortable level of about 40 to 70%, and to produce a functional wallpaper having both flexibility and good appearance. . Here, having flexibility means that it does not break even when bent at 180 °. From the viewpoint of flexibility, the glass transition temperature of the organic resin in the emulsion is more preferably −30 ° C. or lower.

In the case of an inorganic porous material having a large total pore volume, a large amount of water is required when adjusting the water content to obtain a preferable viscosity as a coating composition. Energy is required, production becomes substantially difficult, and there is a problem that cracks are easily generated in the moisture absorbing / releasing layer when a large amount of moisture is dried, but by mixing with the non-porous filler, Such a problem can be solved.
In the present invention, a non-porous filler refers to one having a total pore volume of less than 0.05 ml / g. The shape may be any of a sphere, a polyhedron, a flake, and a needle. Since the non-porous filler does not absorb water when performing moisture control to obtain a preferable viscosity as a coating composition, the non-porous filler facilitates water control of the coating composition, and absorbs and releases moisture when drying the coating film. Has the effect of suppressing the occurrence of cracks.

Further, in a preferred aspect of the present invention, the average particle size of the inorganic porous body is set to 20 to 60 μm.
When the average particle size of the inorganic porous material is 20 μm or more, no cracks are generated, and when the average particle size is 60 μm or less, there is almost no unevenness on the surface and a good appearance can be obtained.

Further, in a preferred aspect of the present invention, the non-porous filler has an average particle size of 5 to 60 μm.
If the average particle size of the non-porous filler is 5 μm or more, no cracks will be generated, and if the average particle size is 60 μm or less, there will be almost no unevenness on the surface and a good appearance will be obtained.

Further, in a preferred embodiment of the present invention, the particle size of the organic emulsion is smaller than the particle size of the inorganic porous material, and the average particle size is 0.2 μm or more.
If the particle size of the emulsion is less than 0.2 μm, the emulsion becomes dense, adjacent emulsions may start to fuse with each other, and may block the permeation route to the inorganic porous material. Therefore, in this case, the moisture absorption / release properties are reduced.
If the particle size of the organic emulsion is too large, the packing ratio of the inorganic porous material is reduced, which may lower the moisture absorption / release performance. Therefore, the particle size of the particles in the emulsion is desirably less than 1 μm.
By doing so, the flexibility as wallpaper can be obtained as good as that of ordinary vinyl cloth, and good moisture absorption / release properties can be exhibited without blocking the pores of the inorganic porous material.

Further, in a preferred embodiment of the present invention, the coating layer has a dry weight of 50 to 500 g / m ² . If it is less than 50 g / m ² , the moisture absorption / desorption property is not sufficiently exhibited to adjust the relative humidity of the space comfortably, and if it is more than 500 g / m ² , the weight per unit area becomes too large, and the workability as wallpaper increases. Problems arise.
Further, within this range, a coating method using a comma coater similar to the production of ordinary vinyl cloth can be used, which is desirable in production.

Further, in a preferred embodiment of the present invention, 0.1 to 5 parts by weight of an antibacterial agent or a fungicide is added to 100 parts by weight of the composition.
By doing so, not only the antifungal property caused by the moisture absorption and release properties of the functional wallpaper of the present invention, but also the antibacterial property and antifungal property can be imparted to the functional wallpaper of the present invention itself.
In addition, since the material having moisture absorption and release properties as in the present invention is inevitably always in a state of containing water vapor and is also a material that easily generates bacteria and mold, an antibacterial agent is added to the moisture absorption and release layer of the functional wallpaper. Or an antifungal agent, and it is preferable to use an antibacterial agent and an antifungal agent in combination, or to use an agent effective against both bacteria and fungi. These are preferably water-soluble.

In a preferred aspect of the present invention, a second layer composed of inorganic particulate matter and an organic binder is formed over substantially the entire surface of the moisture absorbing / releasing layer. The moisture absorbing / releasing layer in the present invention also adsorbs dirt (especially cigarette tar) floating in the air together with water vapor, and furthermore, the dirt easily penetrates into the moisture absorbing / releasing layer, and the dirt is difficult to wipe off. There is.
Therefore, it is desirable to provide a second layer for preventing contamination so as not to impair the moisture absorption / release performance on the surface of the moisture absorption / release layer.

By forming the second layer as described above, it is possible to prevent the permeation of the dirt stain to a certain extent without substantially impairing the permeation of water vapor, and even if the dirt stain is transmitted and adheres to the moisture absorbing and releasing layer. Also, since the second layer in which the inorganic particulate matter is fixed by the organic binder is formed thereon, the dirt attached to the moisture absorbing / releasing layer is not conspicuous, and it is possible to impart antifouling property having no problem in appearance. it can.
A portion where the second layer does not exist has a structure in which the stain is easily adhered to the moisture absorbing / releasing layer, and the adhered stain becomes conspicuous. Therefore, it is desirable that the moisture absorbing / releasing layer is covered over substantially the entire surface. The term “substantially all over” specifically means a state in which 90% or more of the moisture absorbing / releasing layer is covered. Even if there is a part that is not covered in a very small part, there is no practical problem.
If the amount of the organic binder is more than 30 parts by volume with respect to 100 parts by volume of the inorganic particles, sufficient adhesion to the lower layer can be obtained. If the amount is more than 300 parts by volume, the concealing property is reduced. If the thickness of the second layer is increased to provide concealment, the moisture absorption / desorption performance is lowered, and this is not desirable from the viewpoint of cost.

In a preferred aspect of the present invention, the inorganic particulate matter contains any of titanium oxide and calcium carbonate.
Titanium oxide and calcium carbonate, as widely used as pigments, are white materials having excellent concealing properties.
Therefore, even if the stains are adsorbed on the moisture absorbing and releasing layer, the use of titanium oxide and calcium carbonate, which are excellent in concealment properties, makes the stains adhered to the absorbing and releasing layer less conspicuous. In addition, it is advantageous to form the second layer with a white material such as titanium oxide or calcium carbonate in forming a design thereafter. Further, a coloring pigment can be added to the second layer, and the second layer can also serve as a design layer. Further, a design layer may be further formed on the surface of the second layer provided with the design.

  In a preferred embodiment of the present invention, a design layer is formed on the moisture absorbing / releasing layer or the second layer. Here, the design layer is a layer for providing a pattern. The design layer can be formed on the moisture absorbing / releasing layer in the same manner as in the production of ordinary vinyl cloth. Specifically, a gravure printing method by impregnating the moisture absorbing / releasing layer with the ink, a formation of a foam printing layer on the moisture absorbing / releasing layer by a screen printing method, and the like can be used.

  In a preferred embodiment of the present invention, by using foam printing for the design layer, the design can be imparted, and at the same time, the effect of the moisture absorption / release layer as a contamination prevention layer can be exerted in the same manner as the second layer.

In a preferred aspect of the present invention, the area coverage of the foam print layer with respect to the moisture absorbing / releasing layer is set to 60% or more.
By doing so, the function as a contamination prevention layer is sufficiently exhibited.

  In a preferred aspect of the present invention, a deodorant is added to the foam print layer. Since the moisture absorbing / releasing layer of the present invention is made of an inorganic porous material, it has a function of adsorbing and removing not only water vapor but also harmful chemical substances, unpleasant odors, etc. The addition is desirable because the function of adsorbing and removing harmful chemicals and unpleasant odors can be further enhanced.

In a preferred embodiment of the present invention, the photocatalyst is fixed on the outermost layer. For example, when the moisture absorbing / releasing layer is the outermost layer, it is fixed to the moisture absorbing / releasing layer, and when the water repellent layer is the outermost layer, it is fixed to the water repelling layer. At this time, a photocatalyst may be blended in the water-repellent treatment layer, or a photocatalyst layer may be further provided on the surface.
By doing so, a function of decomposing organic substances by light irradiation can be further provided, which is desirable.

In a further preferred aspect of the present invention, the photocatalyst carries an antimicrobial metal.
By doing so, good antibacterial properties are exhibited even in an environment without light irradiation, which is desirable.

In a preferred aspect of the present invention, a coating layer of a dried product of the resin colloidal dispersion is formed on the surface of the design layer.
By doing so, it is possible to form the contamination prevention layer without impairing the moisture absorption / release properties. The resin colloidal dispersion generally has a particle size of 1 to 100 nm, but more preferably 5 to 100 nm.
When the particle diameter is 5 nm or less, the moisture absorption / release performance is impaired. When the particle diameter is 100 nm or more, the gap between the particles becomes large, so that dirt such as cigarette tar passes through and acts as a pollution prevention layer. Is not enough.

In a preferred embodiment of the present invention, a water-repellent layer is formed on the surface of the design layer.
By doing so, it is possible to form a surface that does not easily penetrate water without impairing the permeability of water vapor, and to impart antifouling properties to liquid stains (eg, coffee). Here, the water-repellent layer refers to a layer containing a water-repellent substance such as silicone or fluorine and having a surface angle of 90 ° or more in contact angle with water.

The water-repellent layer is preferably formed on a foam print layer.
By doing so, a particularly good water repellency is exhibited by the synergistic effect of the water repellency due to the unevenness of the foamed print layer and the water repellent treatment, that is, a so-called fractal effect, and the stain resistance to liquid stains is more remarkably exhibited. .

In a preferred aspect of the present invention, the flexible substrate has a three-layer structure of paper, a laminated film, and a nonwoven fabric.
Flexible substrates include paper, synthetic resin sheets, woven fabrics, nonwoven fabrics, glass fiber sheets, metal fiber sheets, flame-retardant backing papers, composite materials of these, laminated materials, and other materials such as vinyl cloth. The substrate that can be used for the wallpaper can be used without limitation, but a particularly preferred embodiment is a three-layer structure in which the flexible substrate is composed of paper, a laminate film, and a nonwoven fabric in order from the back side. The laminate film is a water-impermeable material acting as a waterproof layer, and is made of a synthetic resin such as polyethylene. Since the layer in contact with the moisture absorbing / releasing layer is formed of a nonwoven fabric, good adhesion is obtained due to the anchor effect of the moisture absorbing / releasing layer on the nonwoven fabric.
In addition, it is desirable that the back side surface is formed of paper having water absorption in order to exhibit normal workability as wallpaper.
By making the layer of the water-impermeable laminate film in the middle of these, it is possible to suppress the movement of moisture from the paper to the moisture absorbing and releasing layer during construction, and it is comparable to ordinary vinyl cloth It is desirable from the viewpoint that workability is achieved, and the production of the functional wallpaper of the present invention can also suppress the generation of wrinkles in the moisture absorbing / releasing layer, thereby improving productivity.

In a preferred embodiment of the present invention, the viscosity of the coating solution for forming the moisture absorbing / releasing layer is 4000 to 8000 mPa · s.
By doing so, application by a comma coater similar to the production of ordinary vinyl cloth becomes possible, and good productivity is achieved.
Here, as a method of adjusting the viscosity of the coating solution, a method generally used in viscosity adjustment, such as adjustment by the amount of water added, adjustment by use of an additive such as a dispersant or a thickener, may be used without any particular limitation. Can be.

According to the present invention, while controlling the relative humidity of the space autonomously by absorbing and desorbing water vapor to the inorganic porous body, a function of adsorbing and removing harmful chemicals and unpleasant odors, and having an antibacterial and antifungal function It is possible to efficiently produce and provide inexpensive wallpaper.

Hereinafter, preferred specific embodiments of the present invention will be described.
In the present invention, as an inorganic porous material having a pore volume of 4 to 14 nm and a pore volume of 0.1 g or more, alumina-silica xerogel porous material, silica gel, activated alumina, mesoporous zeolite, mesoporous silica, porous glass, apatite, Examples include diatomaceous earth, sepiolite, allophane, imogolite, and activated clay.
Here, the pore diameter and pore volume can be measured by the Barrett Joyner Halenda method using the desorption isotherm from the measurement result of the adsorption / desorption isotherm by nitrogen gas adsorption.
In the present invention, the total pore volume refers to the total volume of pores that can be measured from the adsorption / desorption isotherm due to nitrogen gas adsorption, and substantially refers to the total volume of pores having a pore diameter of 200 nm or less.
The average particle size of the inorganic porous material is desirably 20 to 60 μm, and is measured by a laser diffraction / scattering type particle size distribution measuring device.

  The inorganic porous body can be selected from commercially available materials and used, and can also be manufactured as follows.

The alumina-silica xerogel porous material is prepared by dissolving aluminum nitrate nonahydrate and tetraethyl orthosilicate in ethanol so as to have a predetermined SiO ₂ / Al ₂ O ₃ ratio, and adding a predetermined amount of water as needed. Prepare solution. After stirring this solution for 3 hours, 25% aqueous ammonia is added to cause coprecipitation and gelation. After rapidly drying the gelled material thus obtained, it is calcined at 300 ° C. for 4 hours to obtain an alumina-silica xerogel porous material.

  Activated alumina can also be adjusted using a method for selectively dissolving kaolin minerals, a pH swing synthesis method, or the like.

  The selective dissolution method will be described. The kaolin mineral is calcined at 900 to 1200 ° C. to cause phase separation into amorphous silica and a spinel layer. Although the calcining temperature depends on the impurities of the kaolin mineral, it is usually preferably 950 to 1050 ° C., and the heating may be further performed for about 1 to 24 hours. By treating the phase-separated material obtained by the heat treatment with an alkali or hydrofluoric acid as described above, the amorphous silica is selectively dissolved, and the dissolved portion is formed as pores. Here, it is particularly preferable to use a KOH aqueous solution of about 1 to 5 mol / l as the alkali treatment. More preferably, by maintaining the composition under heating conditions of about 50 to 150 ° C. for about 1 to 100 hours, the amorphous silica is completely dissolved and pores having a sufficient volume are formed.

  The pH swing synthesis method is a method in which an aqueous solution of an acidic salt and a basic salt of aluminum are mixed and, for example, an acidic salt and a basic salt are alternately added so that pH = 2 and pH = 10, respectively. The acid salt is, for example, aluminum nitrate, and the basic salt is sodium aluminate. The pseudo-boehmite gel formed by mixing these aqueous solutions grows by repeating the pH swing, and the number of swings and the swing pH can be controlled to control the precipitated particle diameter of the pseudo-boehmite gel. By heating and firing the thus obtained pseudo-boehmite gel having a controlled particle diameter, pseudo-boehmite is converted to γ-alumina, and activated alumina in which pores are formed from the particle gap is obtained. Therefore, by controlling the precipitated particle diameter of the pseudo-boehmite gel, the pore diameter of activated alumina after heating and firing can be controlled.

  Organic emulsions include acrylic emulsions, acrylic styrene emulsions, acrylic silicone emulsions, ethylene vinyl acetate emulsions, silicone emulsions, vinyl acetate acrylic emulsions, vinyl acetate emulsions, vinyl acetate veova emulsions, urethane acrylic composite emulsions, silica-modified acrylic copolymer emulsions, Examples include styrene acrylic urethane composite emulsion, ethylene vinyl acetate acrylic composite emulsion, vinyl acetate malate copolymer aqueous emulsion, ethylene-vinyl ester copolymer aqueous emulsion, and fluorine emulsion.

  Examples of the non-porous filler include silica, alumina, titania, zirconia, calcium carbonate, calcium hydroxide, aluminum hydroxide, talc, mica, wollastonite and the like.

In the present invention, as an antibacterial agent and a fungicide to be incorporated in the composition of the moisture absorbing / releasing layer, mainly organic and inorganic agents can be used.
Organic compounds include alcohol, phenol, aldehyde, carboxylic acid, ester, ether, nitrile, peroxide / epoxy, halogen, pyridine / quinoline, triazine, isothiazolone, imidazole / thiazole. Anilide-based, biguanide-based, disulfide-based, thiocarbamate-based, surfactant-based, and organometallic-based compounds.
Examples of the inorganic system include an ozone system, a chlorine compound system, an iodine compound system, a peroxide system, a boric acid system, a sulfur system, a calcium system, a sodium silicofluoroto system, and a metal ion system. Among them, the metal ion type is particularly preferable. Antibacterial metal ions are easier to store and fix in solids than hypochlorous acid, ozone, and the like. In addition, antibacterial metal ions can be taken out from a solid material in which the ions are stored and fixed by controlling the ion elution rate in a necessary amount, so that the antibacterial metal ions can withstand longer-term use. Antibacterial metal ions include silver ions, copper ions, zinc ions and the like.
Substances that release antimicrobial metal ions include silver lactate, silver nitrate, silver acetate, silver sulfate, cuprous acetate, cupric acetate, copper nitrate, cuprous sulfate, cupric sulfate, zinc acetate, zinc nitrate , Zinc chloride, zinc sulfate, and other compounds containing soluble antibacterial metal elements.
Among them, silver ion is superior in effect on bacteria as compared with others, and copper ion is superior in effect on fungi as compared with others. It is desirable to use it.
In addition, for the purpose of controlling the release rate of the antibacterial component, for example, ions of the antibacterial component such as silver, copper, zinc, or the like, or a compound thereof, or a metal simple substance colloid are incorporated into the pores or crystal lattice of the carrier such as an inorganic oxide. A method of supporting is adopted. Examples of the carrier include apatite, calcium phosphate, zirconium phosphate, aluminum phosphate, titania, layered silicate, layered aluminosilicate, zeolite, and the like.
In addition, antibacterial treatment products are often used in living-related environments, so high chlorine resistance is required. Therefore, there is also a method of securing chlorine resistance by using a thiosulfatosilver complex obtained by anionizing silver ions having high reactivity with chlorine.
In addition, natural-derived systems obtained from animals, plants, and the like can be mentioned. Examples include chitin / chitosan, aminoglycoside compounds, hinokitiol, mugwort extract, aloe extract, perilla leaf extract, dokudami, licorice, camellia plant extract, natural sulfur, mustard / wasabi extract, bamboo extract. Can be
Also, a photocatalyst system can be used. Examples include anatase type titanium dioxide, rutile type titanium dioxide, tungsten trioxide, bismuth trioxide, iron trioxide, strontium titanate, tin oxide, zinc oxide and the like. They may be spherical, scaly, fibrous powder or sol.

  In the present invention, the deodorant compounded in the foam print layer includes a porous substance which deodorizes by physical adsorption, and an oxidizing / reducing substance / catalyst substance which deodorizes an odorous substance by a chemical reaction. Examples of the former include activated carbon, impregnated activated carbon, bentonite, silica-magnesia, and the like, in addition to the inorganic porous material described above. Examples of the latter include metal compounds selected from manganese, copper, zinc, cobalt, magnesium, iron, nickel and zinc (for example, sulfate, nitrate, acetate, citrate, organic acid salt, oxide, water Oxides, phthalocyanine complexes, other chelates, etc.), platinum-group metal compounds, iron-manganese-based, titanium-based, silica-alumina-based, metal oxide-based photocatalysts and other inorganic materials, organic amines, artificial Enzymes, inclusion compounds such as cyclodextrins and crown ethers, and plant extracts such as phytonchit, flavonoids, tannins, catechins, essential oils and the like can be mentioned.

  As the photocatalyst used in the present invention, titanium oxide, zinc oxide, strontium titanate, tin oxide, vanadium oxide, tungsten oxide, or the like can be used. In particular, titanium oxide is preferable from the viewpoint of the stability of the material itself, photocatalytic activity, availability, and the like, and it is particularly preferable that the crystal form is anatase.

  Gold, silver, copper, zinc, or the like can be used as the antibacterial metal supported on the photocatalyst.

  As the resin colloidal dispersion used in the present invention, acrylic, acrylic styrene, acrylic silicone, ethylene vinyl acetate, silicone, vinyl acetate acrylic, vinyl acetate, vinyl acetate veova, urethane acrylic, styrene acrylic urethane composite system, ethylene vinyl acetate acrylic composite system And colloidal dispersions such as vinyl acetate malate copolymer, ethylene-vinyl ester copolymer, fluorine and fluoroacrylate.

  In the present invention, as a method for forming the water-repellent treatment layer, an olefin-based, silicone-based, fluorine-based or other water-repellent resin, wax, or the like can be used.

The use of the functional wallpaper of the present invention is typically used for building interior materials such as walls, floors, ceilings, and the like, but can be widely used for interior materials of vehicles such as cars, trains, ships, and aircraft. it can.

Hereinafter, the present invention will be described more specifically with reference to examples.
Physical properties of the inorganic porous material were measured by the following methods.
Measurement of pore diameter and pore volume: The nitrogen gas adsorption / desorption isotherm of each sample was measured, and the pore diameter and pore volume were measured by the Barrett Joyner Halenda method using the desorption side isotherm. For the measurement, a specific surface area / pore distribution measuring device (ASAP2000: manufactured by Micromeritics Co., Ltd.) was used. In the measurement, about 0.2 g of the sample was used. As a pretreatment, heating and degassing were performed at 110 ° C. until the pressure became less than 10 ⁻³ Torr, thereby removing adsorbed components such as water vapor.
Measurement of average particle size of inorganic porous material: A laser diffraction / scattering type particle size distribution measuring device (Laser Micron Sizer LMS-30 manufactured by Seishin Enterprise) was used.

The physical properties of the organic emulsion and the resin colloidal dispersion were measured by the following methods.
Measurement of average particle size of organic emulsion: A laser diffraction / scattering type particle size distribution measuring device (Laser Micron Sizer LMS-30 manufactured by Seishin Enterprise) was used.
Measurement of average particle size of resin colloidal dispersion: A micro trap UPA150 manufactured by Nikkiso Co., Ltd. by a dynamic light scattering method was used. Note that the average particle size is based on number conversion.

Measurement of glass transition temperature of organic emulsion and resin colloidal dispersion: Calculated by the following equation using the glass transition temperature of homopolymer.
n
1 / Tg = Σ (Wi / Tgi)
i = 1
Tg: Tg of copolymer (K)
Tgi: Tg (K) of homopolymer of copolymerized monomer
Wi: weight fraction of the copolymerized monomer The Tg of the homopolymer uses the standards of the Emulsion Industry Association.

(Example 1)
[Production of functional wallpaper]
As a flexible substrate, a base paper for a wallpaper having a three-layer structure of a backing paper, a laminated film, and a nonwoven fabric was used.
As the inorganic porous material, commercially available activated alumina [NEOBEAD-GB manufactured by Mizusawa Chemical Industry Co., Ltd.] was pulverized with a jet mill to adjust the average particle size to 30 μm.
The pore volume of the inorganic porous material after the pulverization was 4 to 14 nm, the pore volume was 0.46 ml / g, and the total pore volume was 0.50 ml / g.
As the organic emulsion, a commercially available acrylic emulsion [Boncoat 3625 manufactured by Dainippon Ink and Chemicals, Inc.] was used. The glass transition temperature of the emulsion was -43 ° C, and the average particle size of the emulsion was 0.2 µm.
After blending as shown in Table 1, after kneading with a kneader, a moisture absorbing / releasing layer was formed with a comma coater so that the weight after drying was 300 g / m ² to obtain a functional wallpaper.

(Example 2)
As in the case of Example 1, a base paper having a three-layer structure of a backing paper, a laminate film, and a nonwoven fabric was used as a flexible base material.
Gelatin akaolin, a clay mineral, is calcined at 1000 ° C. for 2 hours, and the amorphous silica layer is phase-separated, and then treated with 3 mol / l KOH at 90 ° C. for 2 hours to selectively dissolve the amorphous silica layer did. After drying, the average particle size was adjusted to 30 μm by a jet mill, and an inorganic porous material sample 1 was obtained. The pore volume of the obtained inorganic porous material having a pore diameter of 4 to 14 nm was 0.65 ml / g, and the total pore volume was 0.7 ml / g.
The same organic material emulsion as in Example 1 was used, and after blending as shown in Table 2, a functional wallpaper was obtained in the same manner as in Example 1.

(Example 3)
As in the case of Example 1, a base paper having a three-layer structure of a backing paper, a laminate film, and a nonwoven fabric was used as a flexible base material.
As the inorganic porous material, a commercially available porous silica material was used.
The inorganic porous body had an average particle size of 25 μm, a pore volume of 4 to 14 nm having a pore volume of 0.97 ml / g, and a total pore volume of 1.21 ml / g.
As the non-porous inorganic filler, alumina hydroxide having an average particle size of 30 μm was used.
The same organic substance emulsion as in Example 1 was used. After blending as shown in Table 3, a wallpaper was obtained in the same manner as in Example 1.

(Comparative Example 1)
As in the case of Example 1, a base paper having a three-layer structure of a backing paper, a laminate film, and a nonwoven fabric was used as a flexible base material.
As the inorganic porous material, commercially available mesoporous silica [NIPGEL-AZ200 manufactured by Nippon Silica Industry Co., Ltd.] was used.
The inorganic porous body had an average particle size of 2.2 μm, a pore volume of 4 to 14 nm having a pore volume of 0.41 ml / g, and a total pore volume of 2.10 ml / g.
The same organic substance emulsion as in Example 1 was used. After blending as shown in Table 4, a wallpaper was obtained in the same manner as in Example 1.

(Comparative Example 2)
As in the case of Example 1, a base paper having a three-layer structure of a backing paper, a laminate film, and a nonwoven fabric was used as a flexible base material.
The same inorganic porous material as in Example 1 was used.
As the organic emulsion, a commercially available ethylene vinyl acetate emulsion [Licabond BE-920 manufactured by Chuo Rika Kogyo Co., Ltd.] was used. The glass transition temperature of the emulsion was 0 ° C., and the average particle size of the emulsion was 0.7 μm.
These were blended as shown in Table 5, then kneaded with a kneader, and then formed a moisture absorbing / releasing layer with a comma coater so that the weight after drying was 300 g / m ² to obtain a wallpaper.

(Comparative Example 3)
As in the case of Example 1, a base paper having a three-layer structure of a backing paper, a laminate film, and a nonwoven fabric was used as a flexible base material.
As the inorganic porous material, a commercially available diatomaceous earth [Radiolite # 200 manufactured by Showa Chemical Industry Co., Ltd.] was used. The inorganic porous body had an average particle size of 20 μm, a pore volume of 4 to 14 nm in pore volume of 0.0005 ml / g, and a total pore volume of 0.0005 ml / g.
The same organic substance emulsion as in Example 1 was used, and after blending as shown in Table 6, a wallpaper for Comparative Example was obtained in the same manner as in Example 1.

(Example 4)
[Preparation of functional wallpaper containing antibacterial and antifungal agent]
As a flexible substrate, a base paper for a wallpaper having a three-layer structure of a backing paper, a laminated film, and a nonwoven fabric was used.
As the inorganic porous material, commercially available activated alumina [NEOBEAD-GB manufactured by Mizusawa Chemical Industry Co., Ltd.] was pulverized with a jet mill to adjust the average particle size to 30 μm.
The pore volume of the inorganic porous material after the pulverization was 4 to 14 nm, the pore volume was 0.46 ml / g, and the total pore volume was 0.50 ml / g.
As the organic emulsion, a commercially available acrylic emulsion [Boncoat 3625 manufactured by Dainippon Ink and Chemicals, Inc.] was used. The glass transition temperature of the emulsion was -43 ° C, and the average particle size of the emulsion was 0.2 µm.
As the antibacterial and antifungal agent, a commercially available antibacterial and antifungal agent [San Aisol 200 manufactured by San-ai Sekiyu KK] was used.
After blending as shown in Table 7, after kneading with a kneader, a moisture absorbing / releasing layer was formed with a comma coater so that the weight after drying was 300 g / m ^2, and a functional wallpaper containing an antibacterial and antifungal agent was added. Got.

(Comparative Example 4)
A commercially available vinyl cloth was used as a comparative sample of antibacterial and antifungal properties.

(Example 5)
A functional wallpaper was produced in the same manner as in Example 4.
Then, a coating solution prepared based on the composition shown in Table 8 was formed into a film by screen printing so that the thickness of the dried second layer became 10 μm, and then dried at 150 ° C. to prepare a sample.
Titanium oxide and calcium carbonate were used as inorganic particulates. The average particle diameter of titanium oxide was 5 μm, and the average particle diameter of calcium carbonate was 3 μm.
As the organic binder, an organic emulsion (ethylene vinyl acetate) was used.
The glass transition temperature of the organic emulsion used was 0 ° C.

(Example 6)
A functional wallpaper was produced in the same manner as in Example 4.
Then, after coating the foam printing paint having the composition shown in Table 9 by screen printing, the foam was heated at 150 ° C. to foam the paint, and a functional wallpaper having a design layer was obtained.

(Example 7)
A functional wallpaper was produced in the same manner as in Example 4.
Next, a water repellent agent having the composition shown in Table 9 was coated by screen printing to obtain a functional wallpaper having a water repellent layer formed thereon.

(Example 8)
In the same manner as in Example 6, a functional wallpaper having a design layer was produced.
Next, a water repellent agent having the composition shown in Table 10 was coated by screen printing in the same manner as in Example 7 to obtain a functional wallpaper having a water repellent layer formed on the surface of the design layer.

(Example 9)
Then, a functional wallpaper having a resin colloidal dispersion coating layer was coated using gravure printing with a resin colloidal dispersion coating agent having the composition shown in Table 11 to prepare a functional wallpaper. Obtained.
The average particle size of the colloidal dispersion was 30 nm, and the glass transition temperature was 19 ° C.

[Evaluation method]
(1) Evaluation of appearance of film formation state The film formation state of the moisture absorption / release layer was visually evaluated. ○ (good), △ (somewhat poor), × (bad)
(2) Evaluation of flexibility The obtained wallpaper was bent at 180 degrees, and the appearance of the bent portion was visually evaluated. ○ (no crack), △ (partially cracked), × (many cracks)
(3) Measurement of moisture absorption / release properties Measurements were made only for those having good film-forming state and good flexibility.
First, the measurement sample is equilibrated in a thermo-hygrostat at 23 ° C. and 33% RH. Next, the sample is put into a thermo-hygrostat at 23 ° C. and 93% RH, and the amount of absorbed moisture is measured for 24 hours. Then, it was placed in a constant temperature and humidity chamber of 23 ° C. and 33% RH, and the amount of released moisture was measured.
The evaluation results were calculated as a moisture absorption amount [g / m ² ] per unit area and a moisture release amount [g / m ² ].
(4) Evaluation of antibacterial properties Only those having good film-forming state and good flexibility were tested.
Antibacterial evaluation was performed according to the film adhesion method specified in JIS Z2801. According to JIS Z 2801, Staphylococcus aureus was used as a Gram-positive bacterium and Escherichia coli was used as a Gram-negative bacterium. All the methods for judging the results were based on JIS Z 2801, and an antibacterial activity value of 2.0 or more was judged to be antibacterial.
(5) Evaluation of fungicidal properties Only a film having a good film-forming state and good flexibility was tested.
The test was conducted in accordance with the nutrient addition wet method among the mold prevention test methods specified by the Japan Health Housing Association.
The strain was performed using Aspergillus niger.
All the results were determined in accordance with the mold prevention test method specified by the Japan Health Housing Association, and determined according to the following criteria.
5: No growth was observed even under a 40 × microscope without hyphal growth.
4: No hyphal growth was observed with the naked eye, and slight hyphal growth was observed under a 40 × microscope.
3: Intermittent growth is observed with the naked eye, and growth of hyphae is remarkably observed under a microscope of 40 ×.
2: Mold colonies are clearly visible to the naked eye on one half of all test surfaces.
1: Mold growth was clearly visible to the naked eye, and the growth of the mold was expanded on all the test surfaces.
(6) Tobacco stain evaluation test Only those having good film-forming state and good flexibility were tested.
A sample (5 × 5 cm) was stuck to the side of a box having a predetermined volume (volume: 3600 cm ³ , only the lower part was opened), smoke of tobacco was put in from the lower part of the box, and the contamination state before and after the adhesion of tar was evaluated by color difference. Five mild seven cigarettes manufactured by Japan Tobacco Inc. were used for the test. The color difference was measured with a color difference meter ND-300A manufactured by Nippon Denshoku Industries Co., Ltd.
(7) Liquid stain evaluation test
The measurement was performed only for those having a good film-forming state and good flexibility.
A contaminant was dropped on the sample surface, and after 24 hours, a wiping test was performed with a JK wiper (trade name: 150-S, manufactured by Crecia Corporation). If no trace of dirt is removed by wiping with water, dirt will not be removed by wiping with water. Δ, when any trace of dirt still remained, the evaluation result was indicated by ×.
Coffee was used as the pollutant.
(8) Measurement method of contact angle The contact angle when 10 μl of distilled water was dropped on the sample surface was measured. The measurement was performed using a contact angle measuring device CA-X manufactured by Kyowa Interface Chemical Co., Ltd.
(9) Method for measuring harmful gas adsorption characteristics and deodorization characteristics
The measurement was performed only for those having a good film-forming state and good flexibility.
The sample was cut to 15 cm × 10 cm and sealed in a 3 liter Tedlar bag. Hazardous chemical gas and various unpleasant odors were injected into the container, and after a predetermined time, the gas concentration was measured with a detector tube. Formaldehyde was used as the harmful chemical gas, and ammonia was used as the unpleasant odor.
The initial concentration of formaldehyde was set to 20 ppm, and the concentration after 60 minutes was measured.
The initial concentration of ammonia was set to 20 ppm, and the concentration after 60 minutes was measured.

[Evaluation results]
Table 12 shows the evaluation results. As is clear from Table 12, the product of the present invention is excellent in appearance, flexibility, and moisture absorption / release properties. In Comparative Example 1, a large number of cracks occurred, and no flexibility was obtained. In Comparative Example 2, the appearance was good, but no flexibility was obtained. In Comparative Example 3, although both appearance and flexibility were sufficient as a wallpaper, the moisture absorption / release properties were almost the same as those of a vinyl cloth.

As is clear from Table 13, the product of the present invention in which the antibacterial and fungicide was blended in the moisture absorbing / releasing layer had good effects without being affected by the formation of the design layer on the surface and the formation of the water-repellent layer. Antibacterial and antifungal properties were obtained.
On the other hand, in Comparative Examples 3 and 4, no antibacterial property or antifungal property was observed.

As is clear from Table 14, the product of the present invention has a high contact angle, and good results were obtained particularly for liquid stains. Further, those formed with a second layer containing inorganic particulates as represented by Example 5, and those formed with a foamed screen printing layer as represented by Examples 6 and 8, Good results were also obtained. In addition, as is clear from the results of the contact angle measurement, particularly good water repellency was obtained in the case where the water-repellent treatment layer was further formed on the surface of the foamed screen layer.
On the other hand, Comparative Examples 3 and 4 were relatively good for tobacco stains, but had a low contact angle, adhered liquid stains, and could not be completely removed.

  As is clear from Table 15, the product of the present invention showed good results in both harmful gas adsorption and deodorization performance, but in Comparative Examples 3 and 4, almost no harmful gas adsorption and deodorization performance was recognized.

Claims (19)

On the surface of a flexible substrate, the volume of pores having a pore diameter of 4 to 14 nm measured by nitrogen gas adsorption is 0.1 ml / g or more, and all pores having a pore diameter of 1 to 200 nm A functional wallpaper having a moisture absorbing / releasing layer formed of a dried product of a composition containing an inorganic porous material having a volume of 1.5 ml / g or less and an organic emulsion having a glass transition temperature of -5 to -50 ° C. A functional wallpaper, wherein the composition comprises 200 to 400 parts by weight of an inorganic porous material based on 100 parts by weight of a dry weight of the organic emulsion. On the surface of a flexible substrate, the volume of pores having a pore diameter of 4 to 14 nm measured by nitrogen gas adsorption is 0.3 ml / g or more, and all pores having a pore diameter of 1 to 200 nm. A moisture absorbing / releasing layer is formed of a dried product of a composition containing an inorganic porous material having a volume of 1.8 ml / g or less, a non-porous filler, and an organic emulsion having a glass transition temperature of -5 to -50 ° C. A functional wallpaper, wherein the composition contains 30 to 300 parts by weight of an inorganic porous material and 30 to 300 parts by weight of a non-porous filler with respect to 100 parts by weight of a dry weight of the organic emulsion. A functional wallpaper, wherein the total of the inorganic porous material and the non-porous filler is 100 to 600 parts by weight. The functional wallpaper according to claim 1, wherein the inorganic porous material has an average particle size of 20 to 60 m. The functional wallpaper according to claim 2, wherein the inorganic porous body has an average particle size of 20 to 60 m, and the non-porous filler has an average particle size of 5 to 60 m. The functional wallpaper according to any one of claims 1 to 4, wherein a particle diameter of the organic emulsion is smaller than a particle diameter of the inorganic porous body, and an average particle diameter is 0.2 µm or more. Functional wallpaper according to any one of claims 1 to 5 dry weight of the moisture-absorbing and desorbing layer is characterized by a 50 to 500 g / m ^2. The functional wallpaper according to any one of claims 1 to 6, wherein 0.1 to 5 parts by weight of an antibacterial agent or a fungicide is blended in 100 parts by weight of the composition. The functional wallpaper according to any one of claims 1 to 7, wherein a second layer comprising an inorganic particulate matter and an organic binder is formed over substantially the entire surface of the moisture absorbing / releasing layer. The functional wallpaper according to any one of claims 1 to 8, wherein a design layer is formed on the moisture absorbing / releasing layer or the second layer. The functional wallpaper according to claim 9, wherein the design layer is formed by foam printing. The functional wallpaper according to claim 10, wherein a deodorant is compounded in the foam print layer. The functional wallpaper according to claim 11, wherein the area coverage of the foam print layer with respect to the moisture absorption / release layer is 60% or more. The functional wallpaper according to any one of claims 9 to 12, wherein a coating layer of a dried product of the resin colloidal dispersion is formed on a surface of the design layer. 14. The functional wallpaper according to claim 13, wherein the colloidal dispersion has a particle size of 5 to 100 nm. The functional wallpaper according to any one of claims 1 to 14, wherein a water-repellent treatment layer is formed on the outermost layer. The functional wallpaper according to any one of claims 1 to 15, wherein a photocatalyst is fixed to an outermost layer. 17. The functional wallpaper according to claim 16, wherein an antibacterial metal is carried on the photocatalyst. The functional wallpaper according to any one of claims 1 to 17, wherein the flexible substrate has a three-layer structure of paper, a laminated film, and a nonwoven fabric. The functional wallpaper according to any one of claims 1 to 18, wherein the viscosity of the coating liquid for forming the moisture absorbing / releasing layer is 4000 to 8000 mPa · s.