CN1764536A - Functional member and method for production thereof and fluid to be applied - Google Patents

Abstract

The present invention provides a functional member, which is excellent in terms of a humidity controlling function, a removal function of toxic chemicals and an unpleasant living odor, antifouling properties, stain concealing properties, and flexibility. A functional member is provided with a first layer which is formed on a flexible base material and comprises a dry matter of a mixture comprising an inorganic porous material and an organic emulsion, and a second layer comprising an inorganic filler which is fixed over an approximately entire surface of the first layer by an organic binder, wherein the organic matter in the organic emulsion has a glass-transition temperature of -5 DEG C to -50 DEG C; and the organic binder in the second layer is contained in an amount of 30-300 parts by volume to 100 parts by volume of the inorganic filler.

Description

Functional component, method for its production, and coating solution

Technical field

The present invention relates to a functional member having an excellent air humidity control function of autonomously controlling the relative humidity of a space, removal of harmful chemical substances and discomfort in life, and a method for its manufacture and a coating solution Excellent odor removal function, anti-fouling and dirt masking properties, and excellent flexibility.

Background technique

Humidity-regulating building materials having moisture-absorbing and desorbing properties are known. Air humidity-conditioning building materials are building materials that control the relative humidity of the space autonomously. They can absorb moisture when the humidity is high and release moisture when the humidity is low. In particular, in the living environment in recent years, due to the improvement of heat insulation and airtightness, there is a tendency for moisture to stay indoors, so the necessity of air-humidity-conditioning building materials is increasing.

On the other hand, in recent years, health disorders such as schizkuhouse (sickhouse) caused by indoor environmental pollution caused by harmful chemical substances are becoming a problem. In addition, the desire for removal of unpleasant odors in daily life such as bathroom odors, household waste odors, pet odors, etc. is still strong. Therefore, if the air humidity control building material not only has the ability to absorb and dehumidify, but also can absorb and remove harmful chemicals and unpleasant odors in the indoor air, it can also be said to be an ideal building material. In addition, needless to say, it is also desirable that the surface of such an air-humidity-conditioning building material is not easily stained.

Japanese Patent Application Laid-Open No. 2000-117916 discloses a decorative material in which a permeable film such as polyethylene is laminated on the surface of a moisture-absorbing and desorbing resin layer to impart stain resistance. Also, Japanese Patent Laid-Open No. 2001-1479 discloses a decorative material in which stain resistance is imparted by forming a surface protection layer made of a moisture-permeable polyurethane resin on the surface of a moisture-absorbing and desorbing resin layer.

Japanese Patent Application Laid-Open No. 1-113236 discloses a ceramic plate in which a decorative layer having communicating pores is formed on an air humidity-conditioning layer to improve designability. Also, Japanese Patent Application Laid-Open No. 2000-43221 discloses a decorative material in which a decoratively treated permeable film layer is laminated on a moisture absorbing and desorbing resin layer to improve designability.

Contents of Invention

Now, the inventors know that:

A first layer consisting of a dry mixture of inorganic porous body and specific organic latex (liquid) is formed on a flexible base material, and a certain proportion of inorganic filler and The second layer of organic adhesives, whereby a functional member with excellent air humidity control function, removal function of harmful chemicals and unpleasant odors in daily life, antifouling property, dirt masking property and flexibility can be obtained (Material).

Therefore, the object of the present invention is to provide a functional member (material) which has excellent air humidity control function, removes harmful chemicals, and a coating solution for its manufacture, its manufacturing method and its manufacturing method. Functionality, anti-fouling and dirt masking and flexibility of substances and unpleasant odors in life.

A functional building block according to the invention has:

a flexible base material; and

Formed on the base material, the first layer is composed of a dry product containing a mixture of inorganic porous body and organic latex (liquid);

a second layer in which the inorganic filler is fixed by an organic binder over substantially the entire surface of the first layer,

The glass transition temperature of the organic latex is -5˜-50° C., and relative to 100 volume parts of the inorganic filler, the content of the organic adhesive on the second layer is 30˜300 volume parts.

Also, the manufacturing method according to the functional component of the present invention comprises:

Prepare a flexible base material;

coating the substrate material with a coating liquid containing inorganic porous body and organic latex whose glass transition temperature is -5 to -50°C, and drying it to form the first layer;

applying a mixture of an inorganic filler and an organic binder over substantially the entire surface of the first layer to form a second layer,

The content of the organic binder in the second layer is 30-300 parts by volume relative to 100 parts by volume of the inorganic filler.

In addition, the coating liquid used to form the first layer of the functional member of the present invention contains an inorganic porous body and an organic latex (liquid), and the glass transition temperature of the organic matter in the organic latex (liquid) is -5～-50℃.

Description of drawings

Fig. 1 shows an example of the layer structure of the functional material of the present invention, corresponding to the sample prepared in Example A1. This functional material is formed by forming a first layer 2 on a base material 1 and forming a second layer 3 on the first layer 2 .

Fig. 2 is a graph showing the evaluation results of moisture absorption and desorption performance of samples produced using Examples A1 to A3 and A7 and Comparative Examples A1 and A3 to A5.

3 is a diagram showing the layer structure of the functional member produced in Example A2. The functional member is formed with a first layer 2 and a second layer 3 on a base material 1, and a hydrophobic layer is further formed on the second layer 3. 4 into.

4 is a diagram showing the layer structure of the functional member produced in Example A3. The functional member is formed with a first layer 2 and a second layer 3 on a base material 1, and a pattern layer is further formed on the second layer 3. 5 and the hydrophobic layer 4.

Fig. 5 is the figure that represents the layer structure of the functional member that makes with embodiment A4, and this functional member is formed with first layer 2 and second layer 3 on base material 1, adds antibacterial layer 6 in second layer 3 made.

Fig. 6 is a diagram showing the layer structure of the functional member made in Example A5, the functional member is formed with a first layer 2 and a second layer 3 on the base material 1, and an anti-mold layer is added in the second layer 3 7 into.

7 is a diagram showing the layer structure of the functional member made in Example A6. The functional member is formed with a first layer 2 and a second layer 3 on the base material 1, and a hydrophobic layer is further formed on the second layer 3. Layer 4 is formed by adding photocatalyst 8 to hydrophobic layer 4 .

Figure 8 is a diagram showing the layer structure of the functional member made in Example A7, the functional member is formed with a first layer 2 and a second layer 3 on a base material 1, and a hydrophobic additive is added to the second layer 3 9 made.

9 is a diagram showing the layer structure of a functional member produced in Example A8, the functional member is formed with a first layer 2 on a base material 1, and a colored second layer 10 is further formed on the first layer 2. made.

Fig. 10 is a diagram showing the layer structure of the functional member made in Example A9, the functional member is formed with a first layer 2 and a colored second layer 10 on the base material 1, and on the colored second layer 10 Further form a pattern layer 5 and a hydrophobic layer 4 on it.

FIG. 11 is a diagram showing a layer structure of a material produced in Comparative Example A1, which is formed by forming a first layer 2 on a base material 1 .

FIG. 12 is a diagram showing the layer structure of a material produced in Comparative Example A2, which is formed by forming a first layer 2 on a base material 1 and further forming a water-repellent layer 4 on the first layer 2 .

FIG. 13 is a view showing the layer structure of the material prepared in Comparative Example A3, in which the first layer 2 is formed on the base material 1 and the laminate film 11 is further formed on the first layer 2 .

FIG. 14 is a view showing the layer structure of a material produced in Comparative Example A4, in which a first layer 2 is formed on a base material 1 and a urethane resin 12 is further formed on the first layer 2 .

Detailed ways

functional building blocks

FIG. 1 shows an example of a functional member of the present invention. The functional component according to the present invention includes a base material 1 , a first layer 2 and a second layer 3 . A first layer 2 composed of a dried product containing a mixture of an inorganic porous body and an organic latex is formed on a flexible base material 1 . The glass transition temperature of the organic substance used in the organic latex of the first layer 2 is -5 to -50°C. As a result, the first layer 2 not only has the moisture absorbing and desorbing performance of water vapor, but also has the performance of removing harmful chemical substance gases in the room and unpleasant odors in daily life, and has sufficient flexibility.

On substantially the entire surface of the first layer 2, a second layer 3 in which an inorganic filler is fixed with an organic binder is formed. The content of the organic binder in the second layer 3 is 30-300 parts by volume relative to 100 parts by volume of the inorganic filler. According to the second layer 3, the moisture absorption and desorption performance of water vapor and the adsorption and removal function of pollutants of the first layer 2 can be sufficiently ensured, and the antifouling performance and dirt masking performance against pollutants such as cigarette smoke stains can be realized. That is, the second layer 3 does not impede the permeation of water vapor, but prevents the permeation of pollutants to a certain extent, thereby exhibiting antifouling properties. However, in order to maximize the above-mentioned functions of the first layer 2, the second layer 3 does not completely prevent the passage of pollutants, but allows a certain degree of passage of pollutants. Moreover, even if pollutants such as cigarette smoke stains are adsorbed on the first layer through the second layer, the dirt is covered by the inorganic filler quantitatively contained in the second layer, so that the dirt is not conspicuous. That is, dirt concealment is realized. Thus, according to the present invention, moisture absorption and desorption performance, pollutant removal function, antifouling property, and dirt masking property can be simultaneously realized at low cost. The functional component of the present invention has such a multi-functional multi-layer structure and at the same time has flexibility. Therefore, the functional member of the present invention can be used in a wide range of applications including building interior materials, vehicle interior materials, and the like.

Matrix material

As the base material in the present invention, a flexible base material is used, and it is preferable that the base material has a property of not breaking even when bent at 180°C. As a preferred example, it can be mentioned: paper, synthetic resin cloth, woven cloth, non-woven cloth, glass fiber cloth, metal fiber, flame-retardant backing paper, base material paper for wallpaper, composite or laminated materials of these materials, which are generally used in The base material of other wallpapers such as vinyl fabrics, etc.

In the case where the functional member of the present invention is used as a building wallpaper, it is preferable to use a base material for the wallpaper from the viewpoint of price and productivity, and more preferably a base material made of backing paper, film and non-woven fabric. Base material paper composed of three-layer structure. By forming the first layer on the nonwoven fabric of the base material paper, the adhesiveness of the first layer is improved due to the so-called fixing effect. In addition, by arranging the film between the nonwoven fabric and the base paper, it is possible to prevent wrinkles from being generated on the base material paper when the coating liquid is applied to the base material. As a backing paper, in order to exhibit normal construction properties as a wallpaper, it is preferable to use water-absorbent paper. The film is preferably a water-impermeable laminate film made of a synthetic resin such as polyethylene and functioning as a waterproof layer. By interposing an impermeable laminated film layer between the backing paper and the non-woven fabric, it is possible to suppress the movement of moisture from the paper to the first layer during construction, achieving a workability that is not inferior to ordinary vinyl fabrics. Such base material paper is a combustible material mainly composed of organic matter, and its weight is preferably 150 g/m ² or less from the viewpoint of fire resistance.

level one

The first layer in the present invention is composed of a dried product containing a mixture of an inorganic porous body and an organic latex. The first layer is porous and has a large surface area due to the inorganic porous body, so it has excellent moisture absorption and desorption performance of water vapor, and its function of absorbing and removing harmful substances or unpleasant odors in daily life is also excellent. excellent.

The inorganic porous body of the present invention is not limited as long as it has fine pores capable of absorbing and desorbing moisture by absorbing and desorbing water vapor, but preferred examples include: alumina-silica Xerogel porous body, silica gel, activated alumina, mesoporous zeolite, mesoporous silica, porous glass, apatite, diatomaceous earth, sepiolite, pure phenolic resin, imo Onyx (イモゴライド, imogolite), activated clay, etc.

According to a preferred embodiment of the present invention, it is advisable to have a pore volume with a pore diameter of 4 to 14 nm measured by the nitrogen adsorption of the inorganic porous body at 0.1 ml/g or more, and according to the nitrogen adsorption of the inorganic porous body. The total pore volume with a pore diameter of 1-200nm is preferably 1.51ml/g or less. Accordingly, excellent antifouling property and moisture absorption and desorption performance against smoke stains can be obtained. In particular, within the optimum relative humidity range of about 40 to 70%, the humidity can be adjusted autonomously and efficiently.

The pore diameter and pore volume of the inorganic porous body can be calculated and measured from the measurement results of the adsorption, desorption and desorption isotherms based on nitrogen adsorption, using the desorption isotherm and the Barrett Joyner Halenda method. A specific surface area/pore distribution measuring device used in this method is commercially available, and the pore diameter and pore volume of the inorganic porous body can be measured using such a commercially available device.

According to a preferred embodiment of the present invention, the volume average particle diameter of the inorganic porous body is preferably 20 to 60 μm. The average particle diameter can be measured with a laser diffraction/scattering particle size distribution analyzer. Accordingly, cracks do not occur, the surface has almost no irregularities, and a good appearance can be obtained.

The inorganic porous body in the present invention is available as a commercially available material, but it can also be produced as follows.

An example of a method for producing an alumina-silica xerogel porous body is as follows.

First, aluminum nitrate nonahydrate and tetraethyl orthosilicate were dissolved in ethanol so as to have a predetermined SiO ₂ /Al ₂ O ₃ ratio. At this point, water is added in an appropriate amount as needed to adjust the solution. After stirring this solution for 3 hours, 25% aqueous ammonia was added to cause coprecipitation and gelation. After drying the gelled product thus obtained rapidly, it was calcined at 300° C. for 4 hours to obtain an alumina-silica xerogel porous body.

As an example of the manufacturing method of activated alumina, the selective dissolution method of a kaolin mineral is mentioned. In this method, kaolin minerals are calcined at 900-1200° C., and phase-separated into amorphous silica and spinel layers. Although the sintering temperature depends on the impurities of the kaolin mineral, etc., it is usually preferably 950 to 1050° C., and more preferably, heating is performed for about 1 to 24 hours. The phase-separated material obtained by such heat treatment is treated with alkali or hydrofluoric acid to selectively dissolve amorphous silica, and the dissolved portion forms pores.

At this time, it is preferable to use an aqueous KOH solution of about 1 to 5 mol/L as the alkali treatment. In addition, by keeping under heating conditions of about 50 to 150° C. for about 1 to 100 hours, amorphous silica can be completely dissolved and pores having a sufficient volume can be formed.

As another example of the production method of activated alumina, a pH swing (singing) synthesis method can be mentioned. According to this method, pseudo-boehmite gum is precipitated by mixing an aqueous solution of an acidic aluminum salt and a basic salt. Specifically, this mixing is preferably performed by alternately adding an acidic salt and a basic salt of aluminum so that pH=2 and pH=10. A preferable example of the acidic salt is aluminum nitrate, and a preferable example of the basic salt is aluminate soda. The boehmite glue generated in this way realizes particle growth through repeated pH swings, and the precipitated particle size of the boehmite glue can be controlled by controlling the number of swings and the swing pH. By heating and firing the thus obtained pseudo-boehmite glue with a well-controlled particle size, the pseudo-boehmite glue is γ-aluminized to obtain active aluminum in which fine pores are formed by interstices between the particles. That is, by controlling the precipitated particle size of pseudo-boehmite glue, the pore size of activated alumina after heating and firing can be controlled.

As the organic latex of the present invention, an organic latex obtained by dispersing an organic substance such as a resin having a glass transition temperature of -5 to -50°C in a dispersion medium such as water or alcohol is used. Accordingly, the flexibility of the functional material can be improved. The glass transition temperature of the organic substance is preferably -30°C or below. Preferred examples of organic latex include acrylic latex, acrylic-styrene latex, acrylic-silicone latex, ethylene-vinyl acetate latex, silicone latex, vinyl acetate-acrylate latex, vinyl acetate latex, vinyl acetate-tert. Ethylene carbonate (ベオバ, veova) latex, urethane acrylic latex, silica modified acrylate copolymer latex, styrene-acrylic acid-urethane latex, ethylene-vinyl acetate-acrylate latex, vinyl acetate-apple Ester copolymer water-based latex, ethylene vinyl ester (ethylene vinylester) copolymer water-based latex, fluorine latex, etc.

According to a preferred embodiment of the present invention, relative to 100 parts by weight of the dried organic latex, the inorganic porous body is preferably prepared in an amount of 200 to 500 parts by weight. Accordingly, excellent moisture absorption and desorption performance and flexibility can be obtained.

According to another preferred embodiment of the present invention, relative to 100 parts by volume of the dry latex of the organic matter, the proportion of the mixture used to form the first layer is preferably 400-1200 parts by volume of the inorganic porous body. According to this, excellent moisture absorption and desorption performance is obtained, it is difficult to leave a sticky feeling on the surface after drying, and it is also excellent in flexibility. Therefore, it is possible to autonomously adjust the relative humidity of the space to a comfortable 40% to 70%, and it is possible to manufacture beautiful and fluid functional components.

In addition, according to a more preferred aspect of the present invention, the volume of pores with a pore diameter of 4 to 14 nm measured by nitrogen adsorption of the inorganic porous body is preferably 0.2 ml/g or more, and the volume of pores with a pore diameter of 1 to 200 nm is preferably 0.2 ml/g or more. The pore volume is preferably 1.3 ml/g or less. According to this, since sufficient performance can be obtained against the relative humidity of the self-regulating space, and at the same time, the moisture in the organic latex becomes difficult to fill into the fine pores, so that the coating performance is improved. In addition, when moisture adjustment is performed to obtain optimum viscosity as a coating liquid, a large amount of moisture is not required, so the first layer can be dried efficiently, and the productivity is excellent. Furthermore, it is also possible to prevent cracks from occurring in the first layer during drying. The range of pore volume is preferably 1.0mg/l or below.

According to another more preferable aspect of the present invention, preferably, the first layer further contains a non-porous filler. In the present invention, the term "non-porous filler" means a filler with a total pore volume of less than 0.05 ml/g. The shape of the non-porous filler may be spherical, polyhedral, flake-like, needle-like, or the like. Since the non-porous filler does not absorb water, the moisture adjustment of the coating liquid becomes easy, and the occurrence of cracks in the first layer when the coating film dries is suppressed. Preferable 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 form using the above-mentioned non-porous filler, it is more preferable that the proportion of the mixture for forming the first layer is 400 to 1100 parts by volume of the inorganic porous body, 400 to 1100 parts by volume of the non-porous The amount of the porous filler is 50-500 parts by volume, and the total amount of the inorganic porous body and the non-porous filler is 400-1200 parts by volume. Accordingly, since a large amount of water is not required to adjust the water content of the coating liquid, the first layer can be dried efficiently and the productivity is excellent. In addition, it is also possible to prevent the occurrence of cracks in the first layer during drying.

In addition, in the form using the above-mentioned non-porous filler, the volume of pores with a pore diameter of 4 to 14 nm measured by nitrogen adsorption of the inorganic porous body is preferably 0.4 ml/g or more, and the volume of the pores according to the inorganic porous body The total pore volume of the body with a pore diameter of 1 to 200 nm measured by nitrogen adsorption is preferably 1.6 ml/g or less. According to this, excellent moisture absorption and desorption performance is obtained, it is difficult to leave a sticky feeling on the surface after drying, and it is also excellent in flexibility. Therefore, it is possible to autonomously adjust the relative humidity of the space to a comfortable 40-70%, and it is possible to manufacture beautiful and fluid functional components.

According to a preferred aspect of the present invention, the non-porous filler has a volume average particle diameter of 5 to 60 μm. According to this, cracks do not occur, the surface has almost no unevenness, and a good appearance can be obtained.

According to a preferred aspect of the present invention, the particle size of the organic matter in the organic sol used to form the first layer is smaller than the particle size ratio of the inorganic porous body, and the number average particle size is preferably 0.2 μm or more. This prevents the organic matter in the sol from becoming too dense, ensures a permeation path to the inorganic porous body, and sufficiently secures moisture absorption and desorption properties. The preferred particle size of the organic sol is 0.1 μm or less.

According to a preferred aspect of the present invention, the inorganic porous body is preferably approximately spherical particles. By using substantially spherical particles with good fluidity, the filling rate of the inorganic porous body in the membrane is increased, and the moisture absorption and desorption performance can be improved.

According to a preferred aspect of the present invention, the film thickness of the first layer is preferably 50 to 500 μm. Accordingly, sufficient moisture absorption and desorption performance can be exhibited, and the weight per unit area is suitable, and the fluidity is also suitable for construction. In addition, if the film thickness of the first layer is within this range, it is possible to use a coating method based on the same blade coater (commacoater, commacoater) as the production of ordinary vinyl fabrics, so the productivity is also improved. superior.

According to a preferred aspect of the present invention, 0.1 to 5 parts by weight of an antibacterial agent or antifungal agent is compounded in 100 parts by weight of the mixture before drying for forming the first layer. Accordingly, excellent antimicrobial and antifungal properties can be imparted to the functional member. In particular, since the functional member of the present invention is superior in moisture absorption and desorption performance, it must always be in a state of water vapor, and it is also a material that is prone to bacteria and mold. Therefore, it can be said that it is particularly effective to mix an antibacterial agent or an antifungal agent in the first layer of the functional member. In addition, an antibacterial agent and an antifungal agent may be used in combination, or agents effective against both the antibacterial agent and the antifungal agent may be used.

The bacterial agent and antifungal agent in the present invention may be any of organic and inorganic.

Examples of organic antibacterial agents and antifungal agents include triazole-based, alcohol-based, phenol-based, aldehyde-based, carboxylic acid-based, ester-based, ether-based, nitrile-based, peroxide-epoxy-based, Halogen-based, pyridine-quinoline-based, triazine-based, isothiazolone-based, imidazole-thiazole-based, anilide-based, biguanide-based, disulfide-based, thiocarbamate-based, surfactants Antibacterial and antifungal agents of organometallic systems.

Examples of inorganic antibacterial and antifungal agents include ozone-based, chloride-based, iodide-based, peroxide-based, boric acid-based, sulfur-based, calcium-based, sodium fluorosilicide-based, and metal ion-based agents. Antibacterial and antifungal agents.

According to a preferred aspect of the present invention, metal ion-based agents are preferably used as the antibacterial agent and antifungal agent. Compared with hypochlorous acid or ozone, etc., such antibacterial metal ions are easy to preserve in solid matter, and because only the required amount is taken out according to the control of the dissolution rate of ions here, it is more suitable for long-term use. Preferred examples of antibacterial metal ions include silver ions, copper ions, and zinc ions.

Examples of substances that release antibacterial metal ions include silver lactate, silver nitrate, silver acetate, silver sulfate, cuprous acetate, copper acetate, copper nitrate, cuprous sulfate, copper sulfate, zinc acetate, zinc nitrate, zinc chloride , zinc sulfate and other soluble antibacterial metal element compounds. In particular, since silver ions have an excellent effect on bacteria and copper ions have an excellent effect on fungi, it is preferable to select the two ions appropriately or to use them at the same time. In addition, for the purpose of controlling the release rate of the antibacterial component, etc., it is also possible to load the antibacterial component-silver, copper, zinc, etc. body colloid, etc. Examples of the carrier used above include apatite, calcium phosphate, zirconium phosphate, aluminum phosphate, titanium oxide, layered silicate, layered aluminosilicate, zeolite and the like. In addition, anionized silver thiosulfate complexes can ensure chlorine reactive silver ions.

Other examples of antibacterial agents and antifungal agents include those derived from natural products obtained from animals or plants. Specific examples thereof include chitin, chitosan, aminoglycoside compounds, pagoda alcohol, mugwort extract, aloe extract, perilla leaf extract, bok choy, licorice, camellia plant extract, Natural sulfur, mustard seed and wasabi extract, bamboo extract, etc. In addition, a photocatalyst can also be used. Examples thereof include anatase-type titanium dioxide, rutile-type titanium dioxide, tungsten trioxide, bismuth trioxide, iron trioxide, strontium titanate, tin oxide, zinc oxide, and the like. These can be in the form of spherical, scaly, fibrous powders or sols.

According to a preferred aspect of the present invention, the antibacterial agent and antifungal agent added to the first layer are preferably water-soluble. Accordingly, it is possible to provide a low-cost functional member having air humidity-conditioning performance and exhibiting sufficient antibacterial or antifungal properties in all the layers of the multilayer structure even when the first layer has a high moisture content. That is, by adding a water-soluble antibacterial agent or antifungal agent to the first layer, even if the first layer absorbs water vapor and becomes a state with a high water content, the water-soluble antibacterial agent or antifungal agent also uses the adsorbed water as a medium to diffuse to the surface. The entire first floor. As a result, sufficient antibacterial or antifungal properties can be exhibited in the first layer. Moreover, the water-soluble antibacterial or antifungal agent can also diffuse into other layers than the first layer. As a result, although the antibacterial agent or antifungal agent is added only to the first layer, sufficient antibacterial agent or antifungal agent can be exhibited in all the layers of the functional member. The water-soluble antifungal agent is preferably mainly organic, and specific examples include triazole-based, alcohol-based, phenol-based, aldehyde-based, carboxylic acid-based, ester-based, ether-based, nitrile-based, peroxide-cyclic Oxygen-based, halogen-based, pyridine-based, quinoline-based, triazine-based, isothiazolone-based, imidazole-thiazole-based, anilide-based, biguanide-based, disulfide-based, thiocarbamate-based , Surfactant-based, organometallic-based water-soluble fungicides.

Second floor

The second layer in the present invention is a layer in which an inorganic filler is immobilized with an organic binder on substantially the entire surface of the first layer. The second layer does not hinder the transmission of water vapor, and can prevent the transmission of pollutants such as smoke stains to some extent. In addition, even if pollutants such as smoke stains permeate the second layer and are adsorbed to the first layer, they can be covered by the inorganic filler quantitatively contained in the second layer. Things are not eye-catching. Therefore, the antifouling property and appearance are improved.

The second layer is formed over substantially the entire surface of the first layer, and can improve antifouling properties and appearance over substantially the entire surface of the functional member. Also, in the present invention, substantially the entire surface means covering 90% or more of the first layer.

The second layer of the present invention is 30 to 300 parts by volume relative to 100 parts by volume of the inorganic filler. If it is within this range, sufficient adhesiveness to the lower layer can be obtained, and the concealment property of the dirt adhering to the first layer can be improved, and the appearance can be improved. In addition, it is also advantageous in terms of cost.

According to a preferred aspect of the present invention, the film thickness of the second layer is preferably 1 to 100 μm. If it is within this range, sufficient antifouling properties can be obtained, and there will be little hindrance to the permeation of water vapor, and there will be little influence on the moisture absorption and desorption amount. In addition, it is also advantageous in terms of cost.

According to a preferred form of the present invention, the particle size of the inorganic filler is preferably 60 μm or less. If it is within this range, since the particle gap becomes small, the antifouling effect is favorable, and the surface also becomes smooth externally.

According to a preferred aspect of the present invention, the inorganic filler preferably contains any one of titanium oxide and calcium carbonate. Since these substances are white materials with excellent masking properties, they can effectively cover the smoke stains adsorbed in the first layer. In addition, it is advantageous for imparting appearance to the second layer by forming the second layer with a white material such as titanium oxide or calcium carbonate. In addition, by adding a coloring pigment to the second layer, the second layer can also function as an appearance pattern layer, and a pattern layer can be further formed on the surface of the second layer thus imparted with an appearance pattern.

In a preferred aspect of the present invention, the organic binder is a cured product of organic latex. Accordingly, the second layer can be formed by an industrial and inexpensive method. Here, the term "organic latex" means organic latex in which organic components are stably dispersed in water.

In a preferred aspect of the present invention, the glass transition temperature of the organic substance in the organic latex used for forming the second layer is -10 to 30°C. If the glass transition temperature is -10°C or above, the actual use condition, that is, stickiness around room temperature does not appear, and smoke stains are difficult to adhere to the second layer. In addition, if the glass transition temperature is 30° C. or lower, since the second layer has flexibility, cracks are difficult to enter, and no bending marks are left even in a flexible base material.

In the present invention, as preferable examples of the inorganic filler used in the second layer, in addition to titanium oxide, calcium carbonate, aluminum hydroxide, silicon dioxide, aluminum oxide, zirconium oxide, etc., silica sand, ceramic Natural raw materials such as pulverized products. Examples of coloring pigments include metal oxides such as titanium yellow, spinel green, zinc white, iron oxide, chromium oxide, cobalt blue, and iron black; and metal hydroxides such as alumina white and yellow iron oxide. Ferrocyanide compounds such as cyanide, cyanine, etc.; lead chromate such as yellow lead, zinc chromate, molybdenum red, etc.; sulfides such as zinc sulfide, vermilion, cadmium yellow, cadmium red, etc.; selenium compounds; barite, precipitation Sulfates such as permanent barium sulfate; Carbonates such as calcium bicarbonate and precipitated carbonate; Silicates such as hydrous silicate, clay and ultramarine; Carbon such as carbon black; Aluminum powder, Metal powders such as bronze powder and zinc powder; pearlescent pigments such as mica and titanium oxide; phthalocyanines; azo pigments, etc.

In the present invention, preferred examples of the organic adhesive used for the second layer include organic latex, water-soluble resins, photocurable resins, and the like. Organic latex is particularly preferred from the standpoint of forming the second layer by an industrial, inexpensive method.

Preferred examples of organic latex used in the second layer include acrylic acid, acrylic-styrene ester, acrylic silicone, ethylene-vinyl acetate, silicone, vinyl acetate-acrylate, vinyl acetate-vinyl tert-carbonate , urethane acrylic, silica modified acrylate copolymer latex, styrene acrylic urethane composite system, ethylene-vinyl acetate acrylate composite system, vinyl acetate-malate copolymer, ethylene-vinyl ester copolymer, Emulsions of fluorine, fluoroacrylate, etc.

In a preferred aspect of the present invention, the second layer and/or the water-repellent layer further contain at least one of an antibacterial agent and an antifungal agent, and can further exhibit antibacterial or antifungal properties. The antibacterial agent and antifungal agent used in the second layer and/or the hydrophobic layer may be the same as the antibacterial agent or antifungal agent used in the first layer.

In a preferred aspect of the present invention, the second layer preferably further contains a hydrophobic additive. Accordingly, it is possible to easily obtain a functional member having antifouling properties against smoke stains, moisture absorption and desorption performance, and antifouling properties against liquid soils. The preferred content of the hydrophobic additive in the second layer is 0.1 to 100 parts by weight relative to 100 parts by weight of the inorganic filler.

Preferred examples of hydrophobic additives include silicone-based or fluororesin-based additives, and silicone-based hydrophobic additives include polysiloxane, polymethylsiloxane, and polydimethylsiloxane. In the molecule of oxane, etc., there is a siloxane segment [-Si(R ¹ , R ² )-O-Si(R ¹ , R ² )-O- (where R ¹ , R ² are independent, representing hydrogen atom or alkyl)] or silane segment [-Si(R ³ , R ⁴ )-Si(R ³ , R ⁴ )- (in the formula, R ³ , R ⁴ are each independently representing a hydrogen atom or an alkyl group)] Silicon compounds, silicone resins, etc.

Specific examples of hydrophobic additives for fluororesin systems include organic resins containing fluorine atoms in the raw material monomers, more specifically polytetrafluoroethylene, tetrafluoro-perfluoroalkoxy (Japanese: Tetrafluoroethylene copolymer (PFA resin), polyvinyl chloride trifluoride, polyvinylidene fluoride, polyvinyl fluoride, fluorinated rubber, and other fluorine-based resins, fluorine-based surfactants, and the like. Among them, it is preferable to use a fluorine-based surfactant from the viewpoint of hydrophobic performance.

pattern layer

According to a preferred example of the present invention, it is preferable to further form a pattern layer on the surface of the second layer. The design layer in the present invention is a layer provided with patterns, designs, embossing, etc., and its material is not limited. Formation of the pattern layer can be performed in accordance with a general vinyl fabric production method such as gravure printing method, screen printing method, and the like.

According to a preferred example of the present invention, it is preferable to form the pattern layer according to the foam printing method. According to this, an appearance pattern is provided, and it functions as a pollution prevention layer as a 1st layer similarly to a 2nd layer. As the foaming printing paint, paints conventionally used as printing paints for wallpaper can be used without limitation, and specific examples include paints in which a resin and a foaming agent are mixed.

Preferable examples of resin components include acrylic resin, acrylic-styrene resin, acrylic-silicone resin, ethylene-vinyl acetate resin, silicone resin, vinyl acetate-acrylic resin, vinyl acetate-vinyl tert-carbonate Resin, urethane acrylic composite resin, silica modified acrylate copolymer latex, styrene-acrylic acid-urethane composite resin, ethylene-vinyl acetate acrylate composite resin, vinyl acetate-malate copolymer water-based resin, fluorine resin etc.

As the foaming agent, conventionally used decomposition gas generating foaming agents, expandable capsule foaming agents, and the like can be used. As a good example of a decomposition gas generating blowing agent, azodicarbonamide, dinitrosopentamethylenetetramine, p-toluenesulfonylhydrazide (Paratroinsulhorniluruudradido), benzenesulfonylhydrazide (Benzensho Diluhidradid), sodium bicarbonate, ammonium carbonate, etc., as expandable capsule foaming agents, ethane is contained in microparticles coated with thermoplastic resins such as acrylate, vinylidene chloride, acrylonitrile, and urethane. , butane, pentane, neopentane, n-hexane, heptane and other hydrocarbon volatile expansion components of the blowing agent.

According to a preferred example of the present invention, the area coverage of the first layer of the foam printing layer is preferably 60% or above. According to this, the function as a pollution prevention layer can be fully exhibited.

According to a preferred example of the present invention, it is preferable to mix a deodorant in the foam printing layer. Accordingly, the function of removing harmful chemical substances, unpleasant life odors, and the like can be further improved. Examples of deodorizers include porous substances that deodorize by physical adsorption, redox substances and catalytic substances that deodorize odorous substances by chemical reactions. Examples of porous substances deodorizing by physical adsorption include activated carbon, added activated carbon, bentonite, silica-magnesia, and the like in addition to the above-mentioned inorganic porous substances. Examples of redox substances and catalytic substances include those containing metals selected from manganese, copper, zinc, cobalt, magnesium, iron, nickel and zinc, sulfates, nitrates, acetates, citrates, organic Metal compounds of acid salts, oxides, hydroxides, phthalocyanine complexes or other chelates; platinum group metal compounds; iron-manganese series, titanium series, silica-alumina series, metal oxide series Inorganic substances of catalysts; organic amines; artificial enzymes; inclusion complexes of cyclodextrin and crown ether; phytoncide (phytoncide), flavonoids, tannic acid, catechin, essential oil lamp plants extracts, etc.

According to a more preferable example of the present invention, it is preferable to further form a coating layer of dried resin colloidal dispersant on the surface of the design layer, thereby forming a pollution prevention layer without hindering the moisture absorption and desorption properties. The preferred resin colloidal dispersant has a particle size of 1-100 nm, more preferably 5-100 nm. If the particle size is 5nm or more, the moisture absorption and desorption properties are hardly hindered; if the particle size is 100nm or less, pollutants such as smoke stains are difficult to pass through, and the role as a pollution prevention layer can be obtained. Preferred examples of resin colloidal dispersants include acrylic acid, acrylic acid-styrene, acrylic acid-silicone, ethylene-vinyl acetate, silicone, vinyl acetate-acrylic acid, vinyl acetate, vinyl acetate vinyl tert-carbonate, urine Alkane-acrylic acid, styrene-acrylic acid-urethane composite system, ethylene-vinyl acetate-acrylate composite system, vinyl acetate-malate copolymer, ethylene-vinyl ester copolymer, fluorine, fluorinated acrylate, etc. Resin colloidal dispersant.

Hydrophobic layer

According to a preferred form of the present invention, it is preferable to form a hydrophobic layer on the surface of the second layer or the design layer. In the present invention, the so-called hydrophobic layer refers to a layer whose contact angle with surface water becomes 90 degrees or more. According to this, the water vapor permeability is not hindered, and a surface that is difficult for water to permeate can be formed. Therefore, the antifouling property against liquid stains such as coffee is improved. The formation of the water-repellent layer can be performed by applying a water-repellent agent such as an olefin-based, silicone-based, fluorine-based hydrophobic resin, or wax.

According to a preferred aspect of the present invention, it is desirable that a pattern layer is formed on the surface of the second layer, and a water-repellent layer is further formed on the surface. In addition, according to a more preferable aspect of the present invention, it is preferable that the water-repellent treatment layer is formed on the foam printing layer. Accordingly, relying on the synergistic effect of the hydrophobicity of the unevenness of the foamed printing layer and the hydrophobic treatment, that is, the so-called fractal effect, it can exert particularly good hydrophobicity, and more significantly exert its resistance to liquid dirt. antifouling.

catalyst of light

According to a preferred aspect of the present invention, it is preferable that the outermost layer of the functional material further has a photocatalyst. Examples of such an outermost layer include a second layer, a design layer, and a water-repellent layer. In addition, according to other preferred forms of the present invention, the photocatalyst can also be fixed on the outermost layer of the functional material. Accordingly, it is also possible to impart a decomposition function for adsorbed harmful chemical substances and the like.

Examples of photocatalysts include titanium oxide, zinc oxide, strontium titanate, tin oxide, vanadium oxide, and tungsten oxide. In terms of the stability of the material itself, photocatalytic activity, and availability, etc., titanium oxide is better, and anatase-type titanium oxide is particularly preferred. According to a more preferred form of the present invention, it is preferable to endow the photocatalyst with antibacterial and antifungal properties, and make it support a metal for improving photocatalytic activity. Examples of such metals include gold, silver, copper, zinc, platinum, and the like.

When adding photocatalyst particles to the water-repellent layer, the added amount is preferably 1 to 40 parts by weight with respect to 100 parts by weight of the solid content of the water-repellent layer.

use

The use of the functional member of the present invention is not particularly limited, and a wide range of uses can be considered, but as the most suitable use, building interior materials such as walls, floors, and ceilings, as well as automobiles, trains, ships, aviation The interior decoration materials of vehicles such as machines, preferably building wallpapers.

When the functional component of the present invention is used as building wallpaper, in order to ensure fire resistance, the dry weight of the organic latex used for the first layer is preferably 100 g/ ^m2 or less, and the organic latex used for the second layer is preferably 100 g/m or less. The dry weight is 50g/ ^m2 or less, and the total organic matter weight with matrix material is 300g/ ^m2 or less.

Method for producing functional material and coating solution

In the method for producing a functional member of the present invention, an organic latex containing an inorganic porous body and an organic substance having a glass transition temperature of -5 to -50°C is prepared as a coating liquid for forming the first layer mixture. The coating liquid may further contain a non-porous filler.

Then, the coating solution is coated on the flexible base material and dried to form the first layer. The coating of the coating liquid on the base material can be carried out by dipping method, spin coating method, spraying method, printing method, overflow coating (flood coating) method, and these methods are also Can be used in combination etc. Control of the film thickness of the first layer can be performed by changing the lifting speed in the dipping method, the substrate rotation speed in the spin coating method, or the solid content or viscosity of the coating liquid.

In the case where the coating liquid used to form the first layer is mechanically coated with a knife coater or the like, it is preferable to set the amount of water contained in the coating liquid to 20 parts by weight relative to 100 parts by weight of the solid content. ~80 parts by weight, the viscosity is set to 2000~8000mPa.s. According to this, the first layer can be well coated on the surface of the base material.

The method of drying and hardening the coating liquid for forming the first layer can be carried out by either drying at room temperature or forced heating. Forced heating can be performed by far-infrared heat drying, warm air heat drying, etc., and the drying temperature at this time is preferably 100° C. or higher from the viewpoint of productivity.

Furthermore, a mixture of an inorganic filler and an organic binder is applied over substantially the entire surface of the first layer to form a second layer. The mixture is prepared so that the content of the organic binder is 30-300 parts by volume relative to 100 parts by volume of the inorganic filler.

The application of the mixture for forming the second layer can be performed by a known coating device, but is preferably performed by gravure printing, screen printing and combinations thereof. At this time, the film thickness can be adjusted by the solid content and viscosity of the coating liquid containing the inorganic filler, and can be adjusted by controlling the printing speed. Also, in order to form the second film into a thin film, it is preferably performed by gravure printing.

Examples of preferable diluents for adjusting the solid content and viscosity of the coating liquid for forming the second layer include water, alcohols such as isopropanol and ethanol. In industry, it is preferable to use alcohol diluent, which can further reduce the drying temperature after the coating process and shorten the drying time.

Drying and hardening of the coating liquid for forming the second layer may be performed by either drying at room temperature or forced heating. Forced heating can be performed by far-infrared heat drying, warm air heat drying, etc., and the drying temperature at this time is preferably 100° C. or higher from the viewpoint of productivity.

According to a preferred example of the present invention, it is preferable to further coat and dry the coating solution for the design layer or the hydrophobic layer on the surface of the second layer. The formation of the design layer or the water-repellent layer is preferably carried out by gravure printing method, screen printing method and their combined use, etc., although it can be carried out according to a known coating device. Drying and hardening of the water-repellent layer may be performed by either drying at room temperature or forced heating, but it is preferable to perform forced heating from the viewpoint of productivity. Forced heating can be performed by far-infrared heat drying, warm air heat drying, etc., but the drying temperature at this time is preferably 100° C. or higher in terms of productivity.

Example

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

In the following examples and comparative examples, the measurement methods of the physical property values of raw materials are as follows.

Measurement 1: Measurement of pore diameter and pore volume of inorganic porous materials

For about 0.2 g of the test sample, the pore diameter and pore volume were measured using a specific surface area/pore distribution measuring device (ASAP2000, manufactured by Micromeritics Corporation). This measuring device measures the nitrogen adsorption and desorption isotherms of each sample, and measures the pore diameter and pore volume using the isotherm on the desorption side according to the Barrentt Joyner Halenda method. In addition, before the measurement, the inside of the apparatus was heated at 110°C and degassed to less than 10 ^-3 Torr to remove adsorbed components such as water vapor.

Measurement 2: Measurement of average particle diameter of inorganic porous body and inorganic filler

The volume average particle diameter was measured using a laser diffraction/scattering type particle size distribution analyzer (laser micro-classifier LMS-30, manufactured by Seishin Co., Ltd.).

Determination 3: Determination of bulk density of inorganic porous body, non-porous filling material and inorganic granular matter:

The bulk density was measured using a tap density meter (Tap Density Meter KYT-4000, manufactured by Seishin Co., Ltd.).

Measurement 4: Measurement of average particle size of organic latex

The number average particle diameter was measured using a laser diffraction/scattering type particle size distribution analyzer (laser micro-classifier LMS-30, manufactured by Seishin Co., Ltd.).

Measurement 5: Measurement of average particle diameter of resin colloidal dispersant

The number average particle diameter was measured using Nikkiso Co., Ltd. Microtrap UPA150 by the dynamic light scattering method.

Measurement 6: Calculation of glass transition temperature of organic latex and resin colloidal dispersant

When the organic matter dispersed in the organic latex used in the examples or the resin dispersed in the resin colloidal dispersant used in the examples is a copolymer, the glass transition temperature of the monomer is used to calculate the ratio of the organic matter and the resin according to the following formula: Glass transition temperature Tg.

$\mathrm{<span\; class="notranslate">\; 1</span>}<span\; class="notranslate">\; /</span>\mathrm{<span\; class="notranslate">\; Tg</span>}<span\; class="notranslate">\; =</span>\underset{\mathrm{<span\; class="notranslate">\; i</span>}<span\; class="notranslate">\; =</span>\mathrm{<span\; class="notranslate">\; 1</span>}}{\overset{\mathrm{<span\; class="notranslate">\; no</span>}}{\mathrm{<span\; class="notranslate">\; \&Sigma;</span>}}}<span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; wi</span>}<span\; class="notranslate">\; /</span>\mathrm{<span\; class="notranslate">\; Tgi</span>}<span\; class="notranslate">\; )</span>$

(Tg in the formula: Tg (K) of the copolymer

Tgi: Tg(K) of the comonomer monomer

Wi: weight fraction of comonomer monomer)

As the Tg of the homopolymer of the comonomer monomer, that is, Tgi, the standard of the Japan Latex Industry Association was used.

Measurement 7: Measurement of bulk density of dried organic latex

The dry matter of the organic latex was dried, and the dry matter was measured for bulk density by the Archimedes method. At this time, kerosene was used as a solvent, and it was measured until it was no longer dissolved.

In the following examples and comparative examples, the evaluation methods of the produced functional material samples are as follows.

Test 1: Smoke stain adhesion promotion test of smoke

Prepare a box with only an open bottom and a volume of 3600cm ³ . Samples (5 x 5 cm) were taped to the side of the box. Smoke was put in from the bottom of the box, and the smoke stains were allowed to adhere to the sample for 30 minutes, and the pollution state before and after the smoke stains was measured with a color difference meter (ND-300A, manufactured by Nippon Denshoku Kogyo Co., Ltd.). As cigarettes, 5 JT-manufactured Myldosebun (tar 12mg/stick, nicotine 0.9mg/stick) were used.

Test 2: Determination of moisture absorption and release characteristics

First, a measurement sample is equilibrated in a constant temperature and humidity chamber at 23° C. and 33% R.H. Then, the sample was placed in a constant temperature and humidity chamber at 23° C. and 9% R.H., and the moisture absorption was measured over 24 hours. Then, it was placed again in a constant temperature and humidity chamber at 23° C. and 33% R.H. to measure the amount of moisture release.

Test 3: Pollution resistance evaluation test

A polluting substance was dropped on the surface of the sample (the surface on which the second layer was formed), and after 24 hours, a wiping test was performed with a JK wiper (150-S, manufactured by Crecia Corporation). The evaluation criteria are as follows.

Polluting substances use coffee, soy sauce, water-based blue ink.

⊚: Stains of dirt disappeared by wiping with water.

○: The dirt does not come off after wiping with water, but it contains the original solution of synthetic detergent. After wiping carefully, wipe with water, and dry wipe, the trace of dirt disappears.

×: Even after carefully wiping with synthetic detergent and then wiping with water, there are still traces of dirt after dry wiping.

Test 4: Evaluation of antibacterial properties

Antibacterial evaluation was carried out in accordance with the film sealing method stipulated in JIS Z 2801 (2000). The strains used were in accordance with JIS Z2801 (2000), and Staphylococcus aureus was used as a gram-positive bacterium, and Escherichia coli was used as a gram-negative bacterium. The judgment method of the results is also all based on JIS Z2801, and it is judged that the antibacterial activity value is 2.0 or above to have antibacterial properties.

Test 5: Evaluation of mildew resistance

In the anti-mold test method established by the Japan Healthy Housing Association, the test is carried out based on the nutrient-added wet method. Aspergillus niger was used as the bacterial strain. The judging methods of the results are all based on the anti-mold test method formulated by the Japan Healthy Housing Association. The specific evaluation criteria are as follows.

5: No growth of hyphae, and no growth of hyphae was observed even under a 40-power microscope.

4: There is no mycelial development observed with the naked eye, and slight mycelial development can be seen under a 40-fold microscope.

3: Mycelial development can be seen intermittently with the naked eye, and the development of mycelium can be clearly seen under a 40-fold microscope.

2: It can be clearly confirmed with the naked eye that the mold group occurs on 1/2 of the entire test surface.

1:: The growth of mold was clearly confirmed with the naked eye, and the growth of mold expanded to the entire test surface.

Test 6: Evaluation of Flexibility

The sample was bent at 180 degrees, and the appearance of the bent portion was visually evaluated. The evaluation criteria are as follows.

○: No cracks

△: Partial crack

×: There are cracks on the entire surface

Test 7: Evaluation of Fire Resistance

A cone calorimeter (cone calorimeter) test specified in the Building Standards Act was carried out. The judgment of the results is also in accordance with the Building Standard Law, and 8MJ/m ² or less is considered acceptable.

Test 8: Appearance evaluation of film-forming state

The film-forming state of the first layer was visually evaluated. The evaluation criteria are as follows.

○: Good

△: slightly worse

×: Bad

Test 9: Measurement method of contact angle

The contact angle when 10 µl of distilled water was dropped on the sample surface was measured using a contact angle meter (CA-X type, manufactured by Kyowa Surface Chemical Co., Ltd.).

Example A1

Base paper for wallpapers with a three-layer structure of backing paper, film, and nonwoven fabric is prepared as a base material. The base paper for wallpaper has a weight of 111 g/m ² . Activated alumina was prepared as an inorganic porous body. For this activated alumina, measurements 1 and 2 were carried out. As a result, the pore volume with a pore diameter of 4 to 14 nm was 0.41 ml/g, the total pore volume was 0.50 ml/g, and the average particle diameter was 30 μm. Acrylic latex was prepared as organic latex. Assays 4 and 6 were performed on this latex. As a result, the glass transition temperature was -43° C., the average particle diameter was 0.25 μm, and the active ingredient was 60%.

According to the compounding ratio shown in Table 1, the raw materials were put into a mixing mixer and mixed and stirred to obtain a coating liquid. This coating solution was applied to the base material using a doctor blade coater so that the thickness of the dried first layer would be 350 μm. It was dried at 150° C. to form the first layer. The weight of organic matter after drying was 80 g/m ² .

Table 1

The ratio of the mixture of latex containing inorganic porous body and organic matter Proportion parts by weight Activated alumina acrylic latex dispersant [Floweren TG-750W manufactured by Kyoei Chemical Co., Ltd.] Wetting agent [Floren D-90 manufactured by Kyoei Chemical Co., Ltd.] Defoamer [Aqualen 8020 manufactured by Kyoei Chemical Co., Ltd. ]water 703017.50.50.540

The coating liquid was prepared according to the ratio in Table 2. The first layer of the coating liquid was applied by screen printing so that the dried second layer had a thickness of 10 μm. Next, it was dried at 150° C. to obtain a sample having the layer structure shown in FIG. 1 . The weight of organic matter after drying was 10 g/m ² . Titanium oxide and calcium carbonate are used as inorganic fillers. The average particle diameter of titanium oxide was 5 μm, and the average particle diameter of calcium carbonate was 3 μm. As the organic adhesive, organic latex of ethylene vinyl acetate was used. The glass transition temperature of this organic latex was 0°C.

Table 2 Proportion parts by weight Titanium oxide calcium carbonate organic latex dispersant [Floweren TG-750W manufactured by Kyoei Chemical Co., Ltd.] Wetting agent [Floren D-90 manufactured by Kyoei Chemical Co., Ltd.] Defoamer [Aqualen manufactured by Kyoei Chemical Co., Ltd. 8020] water 10202530.40.210

Example A2

The coating solution was prepared according to the ratio in Table 3. The fluorinated acrylate-based hydrophobic additive Oide KCRDOP from Zintech Co., Ltd. [active ingredient 15% by weight] was diluted with Oide KS solvent from Zintech Co., Ltd., which was composed of isopropanol and water. Sexual additives are used. This coating solution was applied on the second layer of the sample obtained in Example A1 by gravure printing so that the thickness of the second layer after drying was 0.2 μm. Next, it dried at 150 degreeC, and the sample shown in FIG. 3 in which the water-repellent layer was further formed was obtained.

table 3 Proportion parts by weight Fluoroacrylate Hydrophobic Additive Oide KS Solvent 10030

Example A3

A pattern was printed on the second layer of the sample obtained in Example A1 by gravure printing to make a pattern layer. As in Example A2, a hydrophobic layer was formed on the design layer to obtain the sample shown in FIG. 4 .

Example A4

A sample shown in FIG. 5 was produced in the same manner as in Example A1 except that 68.6 parts by weight of the coating solution for forming the second layer was added with silver on zeolite and 3 parts by weight of a commercially available antibacterial agent.

Example A5

A sample shown in FIG. 6 was produced in the same manner as in Example A1 except that 0.5 part by weight of a commercially available triazole antifungal agent was added to 68.6 parts by weight of the coating liquid for forming the second layer.

Example A6

A sample shown in FIG. 7 was produced in the same manner as in Example A2 except that 5 parts by weight of a commercially available photocatalyst titanium oxide powder was added to 130 parts by weight of the coating liquid for forming a water-repellent layer.

Example A7

A sample shown in FIG. 8 was produced in the same manner as in Example A1 except that 5 parts by weight of a fluororesin-based hydrophobic additive was added to 68.6 parts by weight of the coating liquid for forming the second layer.

Example A8

A sample shown in FIG. 9 was produced in the same manner as in Example A1 except that 1 part by weight of phthalocyanine blue was added as a coloring pigment to 68.6 parts by weight of the coating liquid for forming the second layer.

Example A9

On the second layer of the sample obtained in Example A8, a pattern was printed by gravure printing to produce a pattern layer. On this pattern layer, a water-repellent layer was formed in the same manner as in Example A2 to obtain a sample shown in FIG. 10 .

Comparative Example A1

A sample shown in FIG. 11 in which only the first layer was formed was produced in the same manner as in Example A1 except that the second layer was not formed.

Comparative example A2

On the first layer of the sample obtained in Comparative Example A1, a water-repellent layer was formed in the same manner as in Example A2 to obtain a sample shown in FIG. 12 .

Comparative Example A3

In the same manner as in Example A1 except that the second layer was not formed, a sample in which only the first layer was formed was produced. A moisture-permeable and water-repellent film was laminated on the first layer to prepare a sample shown in FIG. 13 . A polyethylene-based porous film (manufactured by Tokuyama Corporation, trade name PORUM PUH35, thickness 35 μm, maximum pore diameter 1.1 μm) was used as the moisture-permeable and waterproof film.

Comparative Example A4

In the same manner as in Example A1 except that the second layer was not formed, a sample in which only the first layer was formed was produced. A water-based urethane resin was coated on the first layer by gravure printing to a thickness of 5 μm after drying, and dried to obtain a sample as shown in FIG. 14 . As the water-based urethane resin, a surface treatment agent for a product named Diplacoat AQW manufactured by Daibai Seikayo Co., Ltd. was used.

Comparative Example A5

A commercially available vinyl fabric was used as a sample.

Tests 1 to 7 were performed on each of the obtained samples of Examples A1 to A9 and Comparative Examples A1 to A5. The result is as follows.

Table 4 Smoke stain ΔE Hygroscopicity (g/m ² ) Moisture release (g/m ² ) coffee soy sauce water-based blue ink Example A1 9.4 100 100 ○ ○ ○ Example A2 8.7 99 99 ◎ ◎ ◎ Example A3 7.6 99 99 ◎ ◎ ◎ Example A4 9.1 98 98 ○ ○ ○ Example A5 8.6 97 97 ○ ○ ○ Example A6 8.8 98 98 ◎ ◎ ◎ Example A7 9.2 99 99 ◎ ◎ ◎ Example A8 7.9 98 98 ○ ○ ○ Example A9 7.6 96 96 ◎ ◎ ◎ Comparative Example A1 22.5 101 101 ○ ○ ○ Comparative example A2 19.7 98 98 ◎ ◎ ◎ Comparative Example A3 12.5 61 58 ◎ ◎ ○ Comparative Example A4 10.5 76 75 ◎ ◎ ○ Comparative Example A5 8.9 8 8 ○ ○ x

Test 1: As shown in Table 4, it can be seen that the samples of Examples A1 to A9 having the first layer and the second layer, compared with the samples of Comparative Examples A1 and A2 not having the second layer, obtained excellent Smoke stain resistance of cigarettes.

Test 2: As shown in Table 4, it can be seen that the samples of Examples A1 to A9 have almost no decrease in moisture absorption and desorption characteristics compared with the sample of Comparative Example A1 having no second layer. In addition, as shown in FIG. 1 , it can be seen that the moisture absorption and desorption rate hardly decreases.

In addition, even in Examples A4 and A5 in which an antibacterial agent or an antifungal agent was added to the second layer, the antifouling properties of smoke stains and the moisture absorption and desorption properties were all good regardless of the addition of the antibacterial agent or antifungal agent. In addition, even in Example A3 in which a design layer was formed between the second layer and the water-repellent layer, in Example A8 in which a coloring pigment was added to the second layer, and in Example A8 in which a design layer and a water-repellent layer were further formed In A9, the smoke stain resistance and moisture absorption and release performance are very good.

In the sample of Comparative Example A3 in which a moisture-permeable waterproof film was laminated and in the sample of Comparative Example A4 using urethane resin, although the smoke stain resistance was exhibited to some extent, the effect was small compared with the example, In addition, the moisture absorption and desorption properties are all reduced. In addition, as can be seen from Fig. 1, the decrease in the moisture absorption and desorption rate is remarkable.

Test 3: As shown in Table 4, it can be seen that the embodiments A2 and A6 in which the hydrophobic layer is formed on the second layer, the embodiments A3 and A9 in which the design layer and the hydrophobic layer are formed on the second layer, and the mixed hydrophobic layer in the second layer In Example A7 of the non-toxic additive, the antifouling property to liquid stains such as coffee is also excellent.

Test 4: Table 5 shows the evaluation results of antibacterial performance.

table 5 example Antibacterial activity value Staphylococcus aureus coliform bacteria Example A4 4.1 6.5 Comparative Example A1 0.1 0.2 Comparative Example A5 0.2 0.1

As can be seen from Table 5, the antibacterial activity value of the sample of Example A4 containing an antibacterial agent greatly exceeded 2.0 against either Staphylococcus aureus or Escherichia coli, and it was confirmed that the antibacterial property was good. On the other hand, antibacterial properties were not observed in the commercially available vinyl fabrics of Comparative Example A1 and Comparative Example A5 in which no antimicrobial agent was blended.

Test 5: Table 5 shows the evaluation results of antifungal performance.

Table 6 example determination Example A5 5: No mycelial development Comparative Example A1 1: Mold develops on the entire test side Comparative Example A5 2: Mold develops on 1/2 of the whole test side

As can be clearly seen from Table 6, in the sample of Example A5 containing an antifungal agent, even under a 40-power microscope, the development of hyphae could not be found, and it was confirmed that the antifungal performance was good. On the other hand, antifungal performance could not be confirmed in the commercially available vinyl fabrics of Comparative Example A1 and Comparative Example A5 which did not contain an antifungal agent.

Test 6; Evaluation of Flexibility

The evaluation results of the samples of Examples A1 to A9 were all "◯" and no cracks.

Test 7: Evaluation of fire resistance

The evaluation results of the samples of Examples A1 to A9 all had a total calorific value of 8 MJ/m ² or less, and the results were all "passed".

Example B1

Base paper for wallpapers with a three-layer structure of backing paper, film, and nonwoven fabric is prepared as a base material. The base paper for wallpaper has a weight of 111 g/m ² . A commercially available triazole antifungal agent was prepared as a water-soluble antifungal agent. Commercially available activated alumina was prepared as the inorganic porous body. For this activated alumina, measurements 1 and 2 were carried out. As a result, the pore volume of 4 to 14 nm was 0.41 ml/g, the total pore volume was 0.50 ml/g, and the average particle diameter was 30 μm. Commercially available acrylic latex was prepared as the organic latex. Assays 4 and 6 were performed on this latex. As a result, the glass transition temperature was -43° C., the average particle diameter was 0.25 μm, and the active ingredient was 60%.

According to the compounding ratio shown in Table 7, the raw materials were put into a mixing mixer and mixed and stirred to obtain a coating liquid. This coating solution was applied to the base material using a doctor blade coater so that the thickness of the dried first layer would be 350 μm. It was dried at 150° C. to form the first layer. The weight of organic matter after drying was 80 g/m ² .

Table 7

Proportion of air humidity-conditioning layer coating composition Proportion parts by weight Activated alumina acrylic latex triazole antifungal agent dispersant [Floweren TG-750W manufactured by Kyoei Chemical Co., Ltd.] wetting agent [Floweren D-90 manufactured by Kyoei Chemical Co., Ltd.] defoamer [Kyoei Chemical Co., Ltd. Chemical Co., Ltd. Aqualen 8020] water 70300.517.50.50.540

The coating solution was prepared according to the ratio in Table 8. On the first layer of the coating liquid, the second layer was formed by applying by screen printing.

Table 8 Proportion parts by weight Titanium Oxide Calcium Carbonate Organic Latex Dispersant Wetting Agent Defoamer Water 10202030.40.210

Next, according to the proportioning in Fig. 9, a foamed printing paint was obtained. After the paint was applied by screen printing, the paint was heated at 150° C. to foam the paint to obtain a functional wallpaper further having a pattern layer formed on the second layer.

Table 9

Proportion of foam printing coating Proportion parts by weight Ethylene-vinyl acetate copolymer latex [Panflex OM4200 manufactured by Kuraray Co., Ltd.] Foaming agent [AZ#3051 manufactured by Otsuka Chemical Co., Ltd.] Titanium carbonate water for calcium carbonate pigment 1006201520

Tests 1, 2, 5 and 6 were performed on the obtained sample of Example B1. The results are as follows.

Test 1: As a result of the smoke stain test, the color difference ΔE ^* was 8.4.

Test 2: The hygroscopicity was 101 g/m ² and the hygroscopicity was 100/m ² .

Test 5: The evaluation of mold resistance was "5".

Test 6: The evaluation of flexibility was "◯" (no cracks).

Comparative Example B1

The first layer was formed in the same manner as in Example B1, except that a commercially available poorly soluble antifungal agent in which copper was immobilized with titanium oxide was used instead of the water-soluble antifungal agent in Example B1, and the formation of the second layer was not performed.

Tests 1, 2, 5 and 6 were performed on the obtained sample of Comparative Example B1. The results are as follows.

Test 1: As a result of the smoke stain test, the color difference ΔE ^* was 15.8.

Test 2: The hygroscopicity was 100 g/m ² and the hygroscopicity was 99/m ² .

Test 5: The evaluation of mold resistance was "1".

Test 6: The evaluation of flexibility was "◯" (no cracks).

Example C1

As the base material, a base paper for wallpaper is prepared with a three-layer structure of a backing paper, a laminated film, and a nonwoven fabric. As the inorganic porous body, commercially available activated alumina was prepared. Measurements 1 to 3 were performed on this activated alumina. As a result, the inorganic porous body had a pore volume of 0.46 ml/g with a pore diameter of 4 to 14 nm, a total pore volume of 0.50 ml/g, and a bulk density of 680 g/L. Commercially available acrylic latex was prepared as the organic latex. For this latex, assays 4 and 6 were carried out. As a result, the glass transition temperature was -43° C., the active ingredient was 60%, the bulk density of the dried product was 1200 g/L, and the average particle diameter was 0.2 μm.

According to the compounding ratio shown in Table 10, the raw materials were put into a mixing mixer and mixed and stirred to obtain a coating liquid. This coating solution was applied to the base material using a doctor blade coater so that the thickness of the dried first layer would be 300 μm. It was dried at 150° C. to form the first layer.

Table 10 Proportion parts by weight (parts by volume) Activated alumina Propylene latex (active ingredient) Dispersant Wetting agent Defoamer Water 75(441)30(100)17.50.50.540

As inorganic granular materials, titanium oxide and calcium carbonate were prepared. When measurement 2 was performed on this inorganic granular material, the average particle diameter of titanium oxide was 5 μm, and the average particle diameter of calcium carbonate was 3 μm. Organic latex (ethylene vinyl acetate) was prepared as an organic adhesive. When measurement 6 was performed on this organic latex, the glass transition temperature was 0°C. Then, according to the compounding ratio in Table 11, the coating liquid was prepared. This coating solution was applied on the first layer by screen printing so that the dried second layer had a thickness of 10 μm. Next, it dried at 150 degreeC, and obtained the functional member in which the 2nd layer was formed on the 1st layer.

Table 11 Proportion parts by weight Activated Alumina Acrylic Latex Organic Latex Dispersant Wetting Agent Defoamer Water 10202030.40.210

Example C2

In the same manner as in Example C1, a functional member in which the second layer was formed on the first layer was produced. Then, according to the proportioning of Table 12, prepare foaming printing paint. After applying the paint by screen printing, it was heated at 150° C. to foam the paint, thereby obtaining a functional member in which a design layer was further formed on the second layer.

Table 12 Proportion parts by weight Ethylene-vinyl acetate copolymer latex [Panflex OM 4200 manufactured by Kuraray Co., Ltd.] Foaming agent [AZ#3051 manufactured by Otsuka Chemical Co., Ltd.] Titanium carbonate water for calcium carbonate pigment 1006201520

Example C3

Similar to Example C2, a functional member in which the second layer and the design layer were formed on the first layer was produced. Then, prepare the hydrophobic treatment agent according to the proportioning in Table 13. After applying the water-repellent treatment agent by gravure printing, a functional member in which the water-repellent treatment agent was further formed on the second layer was obtained.

Table 13 Proportion parts by weight Hydrophobic treatment agent [Asahi Higaide AG-533 from Asahi Glass Co., Ltd.] Thickener (MS Rubber manufactured by Asahi Chemical Industry Co., Ltd.) Water 90.5200

Tests 1 to 3, 6, 8 and 9 were performed on the obtained samples of Examples C1 to C3. The results are shown in the following table.

Table 14 Exterior Flexibility Hygroscopicity (g/m ² ) Moisture release (g/m ² ) Smoke stain ΔE Pollution resistance (degree) Contact angle Example C1 Example C2 Example C3 ○○○ ○○○ 109103102 108101101 8.16.76.4 ◎◎◎ 8492121

Claims (28)

1. A functional component, characterized in that it has: a flexible base material; and A first layer formed on the base material and composed of a dry product containing a mixture of an inorganic porous body and an organic latex; On substantially the entire surface of the first layer, the second layer in which the inorganic filler is fixed by an organic adhesive, Wherein, the glass transition temperature of the organic matter in the organic latex is -5˜-50° C., and the content of the organic adhesive in the second layer is 30˜300 volume parts relative to 100 volume parts of the inorganic filler. 2. The functional member according to claim 1, wherein the film thickness of the second layer is 1 to 100 μm. 3. The functional component according to claim 1 or 2, wherein the particle diameter of the inorganic filler is 60 μm or less. 4. The functional member according to any one of claims 1 to 3, wherein the inorganic filler contains at least any one of titanium oxide and calcium carbonate. 5. The functional member according to any one of claims 1 to 4, wherein the organic adhesive is a cured product of organic latex. 6 . The functional component according to claim 5 , wherein the glass transition temperature of the organic matter in the organic latex used in the second layer is -10 to 30° C. 6 . 7. The functional component according to any one of claims 1 to 6, wherein a pattern layer is further formed on the surface of the second layer. 8. The functional component according to any one of claims 1 to 7, characterized in that a hydrophobic layer is further formed on the surface of the second layer or the surface of the pattern layer. 9. The functional member according to any one of claims 1 to 8, wherein the second layer further contains at least one of an antibacterial agent and an antifungal agent. 10. The functional component according to claim 8 or 9, wherein the hydrophobic layer further contains at least one of an antibacterial agent and an antifungal agent. 11. The functional member according to any one of claims 1 to 10, wherein the second layer further contains a photocatalyst. 12. The functional member according to any one of claims 8 to 11, wherein the hydrophobic layer further contains a photocatalyst. 13. The functional member according to any one of claims 1 to 12, wherein the second layer further contains a hydrophobic additive. 14. The functional member according to any one of claims 1 to 13, wherein the volume of pores in the inorganic porous body with a pore diameter of 4 to 14 nm measured by nitrogen adsorption is 0.1 ml/g Or above, the total pore volume of the inorganic porous body with a pore diameter of 1 to 200 nm measured by nitrogen adsorption is 1.51 ml/g or less. 15. The functional member according to any one of claims 1 to 14, wherein the first layer contains 200 to 500 parts by weight of inorganic porous matter relative to 100 parts by weight of dry matter of organic latex. Body made. 16. The functional component according to any one of claims 1 to 15, characterized in that, the dry weight of the organic latex used in the first layer is 100g/ ^m2 or less, and used in the The dry weight of the organic latex of the second layer is 50 g/m ² or less, and the total organic weight including the base material is 300 g/m ² or less. 17. The functional component according to any one of claims 1 to 16, wherein the first layer further contains a water-soluble antifungal agent. 18. The functional member according to any one of claims 1 to 17, wherein the first layer further contains 400 to 1200 parts by volume of inorganic porous matter with respect to 100 parts by volume of dried organic latex Body made. 19. The functional member according to claim 18, wherein the volume of pores with a pore diameter of 4 to 14 nm measured by nitrogen adsorption in the inorganic porous body is 0.2 ml/g or more, and the pore diameter is The total pore volume of 1 to 200 nm is 1.3 ml/g or less. 20. The functional component according to any one of claims 1 to 17, wherein the first layer further contains a non-porous filler. 21. The functional member according to claim 20, wherein, relative to 100 parts by volume of dried organic latex, the first layer contains 400 to 1100 parts by volume of inorganic porous body and 50 to 500 parts by volume The non-porous filler is formed, and the total amount of the inorganic porous body and the non-porous filler is 400-1200 parts by volume. 22. The functional member according to claim 20 or 21, characterized in that the volume of pores with a pore diameter of 4 to 14 nm measured by nitrogen adsorption in the inorganic porous body is 0.4 ml/g or more, and the inorganic porous body The total pore volume of the porous body with a pore diameter of 1 to 200 nm measured by nitrogen gas adsorption is 1.6 ml/g or less. 23. The functional member according to any one of claims 7 to 22, wherein a coating layer of a dried resin colloidal dispersant is formed on the surface of the pattern layer. 24. The functional member according to any one of claims 1 to 23, wherein a photocatalyst is immobilized on the outermost layer. 25. The functional component according to any one of claims 1 to 24, wherein the base material is selected from paper, synthetic resin cloth, woven cloth, non-woven cloth, glass fiber cloth, metal fiber, barrier Burning lining paper, base material paper for wallpaper, and composite or laminated materials of these. 26. A coating solution, characterized in that, the coating solution is a coating solution for forming the first layer of the functional member according to any one of claims 1 to 25, containing an inorganic porous body Made of organic latex, characterized in that the organic glass transition temperature of the organic latex is -5 to -50°C. 27. The coating liquid according to claim 26, further comprising a non-porous filler. 28. The method for manufacturing a functional component according to any one of claims 1 to 25, said method comprising: prepare a flexible base material; coating the coating liquid according to claim 26 or 27 on the base material, and drying it to form the first layer; applying a mixture of an inorganic filler and an organic binder over substantially the entire surface of the first layer to form a second layer; Wherein, relative to 100 parts by volume of the inorganic filler, the content of the organic binder in the second layer is 30-30 parts by volume.

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