JP2003170543A - Functional sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sheet which has moisture absorbing and discharging functions of high moisture absorptivity/dischargeability, good flexibility, strong strength against folding at the time of conducting, and in which the changing width of the humidity in association with the temperature change of an outside world can be converged. <P>SOLUTION: The functional sheet comprises an inorganic porous material having a pore size of 3 to 12 nm and a pore volume of 0.3 ml/g or more, and a coating of a mixture containing an emulsion of an organic material having a glass transition temperature of -30 to -50°C. Thus, the moisture absorption and the moisture discharge equilibrium of a steam can be autonomously controlled to 50 to 70% of a comfortable humidity range, and the functional sheet having the flexibility can be formed with the good appearance. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a functional sheet having an excellent autonomous humidity control function capable of properly controlling indoor humidity to impart dewproofness and mildewproofness and ensuring a comfortable space. .

[0002]

2. Description of the Related Art In recent years, the living environment is becoming more comfortable as the heat insulation is improved and the heating equipment is improved. There is a case where internal dew condensation occurs and decay fungi multiply and deteriorate the strength of the wall material, and as a result, it becomes impossible to maintain sufficient strength against an earthquake disaster. There are also allergic problems associated with the reproduction of mites and molds. Furthermore, energy consumption will increase in the future, and in addition to cost, it is necessary to reduce the load on the air conditioning equipment in view of global environmental problems.

The above-mentioned artificial environmental control using a heat insulating material, a heater, etc. is intended to perform temperature control in order to comfortably spend the high temperature and high humidity or low temperature and low humidity environmental conditions in Japan. A comfortable environment can be realized by itself. Therefore, the interior material itself has a humidity control function, and the humidity inside the room can be adjusted without the need for air-conditioning equipment or electric power. Development is underway. Calcium silicate building materials (JP-A-5-293367), diatomaceous earth-based building materials (JP-A-4-354514), zeolite-based building materials (JP-A-3-93632), allophane-based building materials (Patent 304)
1348) and so on. In addition to the board-shaped and tile-shaped building materials as described above, various types of sheets having moisture absorbing / releasing properties have been developed, and sheets using a superabsorbent polymer substance (Japanese Patent Laid-Open No. 62-231740, Kaihei 1
0-128892) or a sheet using an inorganic moisture absorbing / releasing material such as zeolite or diatomaceous earth (JP-A-54-1444).
21, JP-A-64-6181, Japanese Patent Publication No. 1-26731,
JP-A-11-58625 and JP-A-11-207853) are disclosed. Although the above-mentioned board-shaped and tile-shaped building materials have a high moisture absorption and desorption capacity, they are poor in workability and expensive, and therefore development of a sheet suitable for reforming is desired.

The hygroscopic effect is achieved by the adsorption of water vapor into the pores of the microporous material. Liquefaction due to gas condensation in the pores and gasification of the liquid occur depending on the pore diameter, and the pore radius where such a state change occurs is called the Kelvin radius based on the Kelvin capillary aggregation theory. , Is determined by the following Kelvin equation. lnP / P0 = -2γV1 / rmRT As is apparent from the Kelvin equation, the position of humidity at which the adsorption amount increases is determined by the size of the pore size. By the way, the range of relative humidity that is comfortable in the living environment is about 50-
Since it is said to be 70%, the Kelvin radius of the pores is about 2 to 6n from the above Kelvin capillary aggregation theoretical formula.
If m, humidity control can be autonomously performed within the range of relative humidity that is most ideally comfortable.

By the way, as described above, various types of moisture absorptive and desorptive sheets have been developed, but the following problems remain. Organic moisture-absorbing and desorbing materials have many problems such as not being able to completely re-release moisture that has once absorbed water, swelling due to water-absorption, or producing mold, so inorganic moisture-absorbing and desorbing materials do not have these drawbacks Materials are preferred.
However, even in the inorganic type, zeolite absorbs moisture to some extent, but since it is inferior in moisture releasing property, it is not necessarily suitable for use as a humidity control building material. The conventional diatomaceous earth has a small pore volume that influences the moisture absorption / release capacity, and has almost no pores having a pore size suitable for controlling in a comfortable humidity range. Recently, Wakkanai diatomaceous earth having a relatively large number of suitable pore diameters was discovered, and board-shaped and tile-shaped building materials using the same have been developed. Also,
A moisture absorptive and desorptive sheet containing the diatomaceous earth produced in Wakkanai is disclosed (JP-A-11-207853).

[0006]

However, the moisture absorptive and desorptive sheet must have sufficient flexibility from the standpoint of construction, especially when it is used as wallpaper, and the thickness of the moisture absorptive and desorptive layer must be limited. I had no choice. On the other hand, the moisture absorption and desorption property is important in terms of the absolute amount of the microporous material as well as the pore diameter and the pore volume of the microporous material, but the conventional sheet is more sufficient than the board-shaped and tile-shaped building materials. The moisture absorbing / releasing effect could not be exhibited. The present invention has a high moisture absorbing / releasing function, and is capable of converging the fluctuation range of humidity due to temperature changes in the external environment, and also has good flexibility, and a sheet having a moisture absorbing / releasing function that is strong against bending during construction. The purpose is to provide.

[0007]

In order to achieve the above object, in the present invention, the surface of a flexible substrate has an average diameter of 3 to 12 nm and a pore volume of 0.3 ml.
/ G or more of inorganic porous material and glass transition temperature of -30 to 30
A functional sheet characterized by being coated with a dried product of a mixture containing an organic emulsion at -50 ° C. As a result, it is possible to autonomously control the moisture absorption / desorption balance of water vapor within a comfortable humidity range of 50 to 70%.
In addition, it is possible to form a functional sheet having both flexibility and good appearance.

In a preferred embodiment of the present invention, the content of the inorganic porous material in the mixture is 200 to 400 parts by weight per 100 parts by weight of the dry emulsion of the organic material. When the content of the inorganic porous material exceeds 400 parts by weight, cracks are likely to occur due to drying shrinkage during molding, and flexibility is poor. On the other hand, the content of the inorganic porous material is 2
If it is less than 00 parts by weight, not only the moisture absorption and desorption performance is inferior, but also because an organic emulsion having a glass transition temperature of −30 to −50 ° C. is used, blocking resistance is inferior and molding becomes difficult.

In a preferred aspect of the present invention, the coating layer of the dried product of the mixture has a film thickness of 300 μm or more. The coating layer of the mixture of the inorganic porous material and the organic emulsion is preferably 300 μm or more, more preferably 500 μm or more and 1 mm or less. By adjusting the thickness of the above film, the absolute amount of the microporous material capable of exerting a sufficient moisture absorbing / releasing effect can be ensured in the coating layer as compared with the board-shaped or tile-shaped building material, and the moisture absorption / release can be secured. Wetting performance and flexibility,
A functional sheet having good crack resistance can be obtained.

In a preferred aspect of the present invention, the inorganic porous material has an average particle size of 30 μm to 60 μm. If the inorganic porous material has an average particle diameter of 30 μm to 60 μm, the film forming property is good. If the average particle size is less than 30 μm, cracks occur, and if the average particle size is more than 60 μm, unevenness occurs on the surface and the appearance is impaired.

In a preferred embodiment of the present invention, the coating agent for coating the surface of the substrate with the mixture of the inorganic porous material and the emulsion of the organic material contains 20 to 40 parts by weight of water per 100 parts by weight of 4000. ~ 5000
It should have a viscosity of mPa. By doing so, a highly homogeneous molded product excellent in mechanical strength can be obtained. Here, the viscosity is measured by using a B type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd., BL type) under a BL adapter and a rotational speed of 12 rpm.

In a preferred embodiment of the present invention, the particle size of the particles in the organic emulsion is smaller than the particle size of the inorganic porous material and has an average particle size of 0.2 μm or more. If the particle size of the emulsion of the organic substance is too small, the emulsion will have a shape in which the periphery of the inorganic porous material is densely enclosed, and the moisture permeable route to the inorganic porous material is blocked. Therefore, in this case, the moisture absorbing / releasing performance is deteriorated. In a more preferred embodiment, the particle size of the particles in the emulsion is preferably less than 1 μm. When the particle size of the organic emulsion is too large, the filling rate of the inorganic porous material is lowered, which may reduce the moisture absorption / release performance. Further, according to the aspect of the present invention, a structure in which a thin film layer of an organic emulsion is formed on the surface of an inorganic porous material is obtained, and superhydrophobicity is exhibited on the surface. The coating structure is such that the inorganic porous body is aggregated with voids, and the surface thereof has a concavo-convex structure, and the organic emulsions coated on the inorganic porous body are also fused and connected to each other, The surface is also a multi-step fine uneven structure having a fine uneven structure. With this structure, it is possible to secure antifouling performance and water resistance performance due to super water repellency on the surface while maintaining the water vapor adsorption performance in the pores of the microporous material. Here, the particle size of the particles in the emulsion is measured by a laser diffraction / scattering particle size distribution measuring device (Laser Micron Sizer LMS-30 manufactured by Seishin Enterprise Co., Ltd.).

In a preferred embodiment of the present invention, the inorganic porous material is substantially spherical particles. By using the substantially spherical particles having good fluidity, the filling rate of the inorganic porous material in the film is increased, and the moisture absorption / release performance can be improved.

In a preferred embodiment of the present invention, pattern processing is performed by a method of pressing a roll having a three-dimensional pattern on the coating layer of the mixture of the above functional sheets. In a preferred embodiment, a step of applying the mixture to the surface of the flexible substrate and a step of drying the coating until the coated coating is in a semi-dried state were performed in this order. After that, a step of patterning is performed by a method of pressing a roll having a three-dimensional pattern on the surface of the coating, and then the coating is completely dried. By doing so, it is also possible to process into a desired handle while having the above-mentioned effects. In this case, the pattern can be sharply expressed by keeping the drying of the pre-processed film in a semi-dry state and pressing the roll.

In a preferred embodiment of the present invention, photocatalyst particles are further carried on the coating layer of the mixture of the above functional sheets. In a preferred embodiment, a step of applying the mixture to the surface of the flexible substrate and a step of drying the coating until the coated coating is in a semi-dried state were performed in this order. After that, photocatalyst particles are applied to the surface of the coating film, and then the coating film is completely dried. By doing so, it becomes possible to impart a photocatalytic function while having the above-mentioned effects.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. In the present invention, the inorganic porous material is, for example, an alumina-silica coprecipitated xerogel porous material, silica gel, γ-
Alumina porous body, mesoporous zeolite, porous glass, apatite, diatomaceous earth, sepiolite, allophane,
At least one selected from imogolite, activated clay and porous silica can be used. The pore diameter is 3 to 12 nm in average diameter, and the pore volume is 0.3 ml / g or more. Here, the average diameter and the pore volume of the pores are measured by a Brrett Joyner Halenda method using a desorption isotherm using a specific surface area / pore distribution measuring device (ASAP 2000, manufactured by Micromeritics). . The average particle size of the inorganic porous material is 30 μm or more.
It is preferably 60 μm. Here, the average particle size of the inorganic porous material is measured by a laser diffraction / scattering particle size distribution measuring device (Laser Micron Sizer LMS-3 manufactured by Seishin Enterprise Co., Ltd.).
Measure with 0).

Of the above substances, the alumina-silica coprecipitated xerogel porous body can be manufactured as follows. That is, aluminum nitrate nonahydrate and tetraethyl orthosilicate are dissolved in ethanol so as to have a predetermined SiO2 / Al2O3 ratio, and at this time, if necessary, a predetermined amount of water is added to adjust the solution. After stirring this solution for 3 hours, 25% aqueous ammonia was added instantaneously to coprecipitate.
It can be gelled and rapidly dried using a rotary evaporator, and the dried gel is calcined at 300 ° C. for 4 hours to obtain an alumina-silica coprecipitated xerogel porous body.

The γ-alumina porous material can be obtained, for example, by calcining a calion mineral and / or an alumina-silica coprecipitated gel and then treating it with alkali or hydrofluoric acid. Kaolin mineral has a general formula: nSiO2
.Al2O3.mH2O, but as such a kaolin mineral, for example, kaolinite (2Si
O2 ・ Al2O3 ・ 2H2O), dickite (2SiO2 ・
Al2O3 ・ 2H2O), Nacrite (2SiO2 ・ Al2O)
3.2H2O), halloysite (2SiO2 ・ Al2O3.4)
H2O), Allophane (1-2 SiO2 ・ Al2O3 ・ 5H2
O), imogolite (SiO2, Al2O3, nH2O, etc.) When this kaolin mineral is heated, kaolin mineral → metakaolin → spinel phase (γ-alumina) +
Phase change from amorphous silica to mullite + cristobalite. Thus, in order to phase-separate the kaolin mineral into the spinel phase and the amorphous silica, it is usually 900 to 1200.
C., preferably at 950 to 1000.degree. C. for 100 hours or less, preferably 1 to 24 hours. For example, when kaolinite from Georgia or halloysite from China is used as the kaolin mineral,
It is preferable to maintain the temperature at about 1000 ° C. for about 1 to 24 hours to prepare a heat-treated product in which the spinel phase and the amorphous silica are phase-separated. When the heat treatment temperature for phase-separating kaolin minerals such as Chinese halloysite is higher than 1200 ° C., γ-alumina disappears because γ-alumina reacts with amorphous silica to form mullite. On the other hand, when the heat treatment temperature of the kaolin mineral is lower than 900 ° C., phase separation into spinel phase and amorphous silica does not occur.
The heat-treated product is treated with alkali or hydrofluoric acid to give γ-
A porous alumina body is manufactured. When a KOH solution having a concentration of about 1 to 5 mol / l is used as the alkali per 1 g of the heat-treated product in the treatment with alkali or hydrofluoric acid,
The temperature is usually 200 ° C. or lower, preferably 25 to 200 ° C., more preferably 50 to 90 ° C., usually 100 hours or less, preferably 1 minute to 100 hours, further preferably 5
It is desirable to hold the time for minutes to 100 hours, particularly preferably for 30 minutes to 5 hours.

When the heat-treated product of kaolin mineral is treated with alkali or hydrofluoric acid, alkali-soluble components such as amorphous silica are selectively dissolved and removed to make it porous. As the alkali, any alkali can be used as long as it exhibits strong alkalinity, such as LiOH, NaOH, KOH, Mg (OH) 2,
An example is Ca (OH) 2. The γ-alumina porous material thus obtained usually shows a sharp peak with a uniform pore size in the vicinity of 2 to 4 nm and a specific surface area of 100 to 35.
High as 0 m ² / g and total pore volume of 0.5-0.9 m
It is as large as 1 / g and can maintain a high specific surface area even at high temperatures.

The organic emulsion includes, for example, acrylic emulsion, acrylic styrene emulsion, acrylic silicone emulsion, ethylene vinyl acetate emulsion, silicone emulsion, vinyl acetate acrylic emulsion, vinyl acetate emulsion, vinyl acetate vaova emulsion, urethane acrylic composite emulsion, silica. Modified acrylic copolymer emulsion, styrene-acryl urethane composite emulsion, ethylene vinyl acetate acrylic composite emulsion, vinyl acetate malate copolymer emulsion, ethylene-vinyl ester copolymer aqueous emulsion, fluorine emulsion, and the like, among which the glass transition temperature- At least one selected from those having a temperature of 30 to -50 ° C can be used. Emulsions of these organic substances have a particularly excellent binder function and are characterized in that a flexible sheet can be obtained without adding a plasticizer or the like. When the glass transition temperature is higher than -30 ° C, the mechanical strength and crack resistance are poor. In addition, it is difficult to realize a flexible sheet having a film thickness or an inorganic porous material content necessary for satisfying the target moisture absorption / release performance described later. On the other hand, when the glass transition temperature is lower than -50 ° C, the blocking resistance is poor. Among the above emulsions of organic substances, the use of silicone emulsion, fluorine emulsion and the like has the effect of enhancing the super water repellent performance described later, since the surface energy is low. Here, the glass transition temperature of the emulsion of the organic substance is calculated by the following calculation formula using the glass transition temperatures of various homopolymers. Here, Tg: Tg (K) of the copolymer, Tgi: Tg (K) of the homopolymer of the copolymerization monomer, and Wi: weight fraction of the copolymerization monomer. The Tg of homopolymer
Uses the emulsion industry association standards.

As the flexible substrate, paper, synthetic resin sheet, woven fabric, non-woven fabric, glass fiber sheet, metal fiber / glass fiber composite sheet, flame-retardant backing paper and the like can be used.

When a material having a moisture absorbing / releasing property or a water permeable property such as paper is used as the substrate, the moisture adsorbed in the moisture absorbing / releasing layer penetrates through the substrate to the back surface (for example, inside the wall). Sometimes. In some cases, the back surface itself may become damp, warped, or have mold or rust due to the water that has penetrated into the back surface. Therefore, when it is necessary to prevent this phenomenon, it is preferable to form a moisture-proof / water-proof layer on the front surface (moisture absorbing / releasing resin layer side), back surface, or both front and back surfaces of the base material. Moisture-proof and waterproof materials include polyethylene, polyvinylidene chloride,
Examples include silica vapor deposition terephthalate. The moisture-proof / water-proof layer is formed by adhering the moisture-absorbing / releasing sheet or a base material coated with the moisture-absorbing / releasing layer with an adhesive, or by applying by a melt extrusion method or the like.

If desired, a decoration may be provided on the moisture absorptive and desorptive layer within a range that does not impair the moisture absorptive and desorptive performance. For decoration,
For example, there is a method of kneading a known pigment into a mixture, or a method of printing a pattern by using an ink and a printing method. In the case of pattern printing, it is desirable to provide it partially rather than on the entire surface.

The functional sheet of the present invention is typically used as an interior material for buildings such as walls, floors and ceilings, but also as an interior material for vehicles such as automobiles, trains, ships and aircraft, and doors. It is also used for fittings such as fusuma, window frames, handrails, chests of drawers, furniture such as kitchens, partitions and containers.

[0025]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The physical properties of the inorganic porous material were measured by the following methods. BET specific surface area, pore diameter, and pore volume measurement: The specific surface area of each sample was measured by the BET method by nitrogen adsorption, and the pore diameter distribution was analyzed using the desorption side isotherm by Brrett Joy.
It was performed by the ner Halenda method. For measurement,
A specific surface area / pore distribution measuring device (Asap 2000, manufactured by Micromeritics) was used. When measuring
About 0.2 g of sample was used. Degassing is 10 ^-3 t at 110 ℃
It carried out for 10 hours until it became less than orr.

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 Co., Ltd.) was used.

Example 1 [Preparation of humidity control sheet sample] As a base material, a basis weight of 65 g
I used the wallpaper base paper. The inorganic porous material is activated alumina [trade name NEOBEAD-GB manufactured by Mizusawa Chemical Industry Co., Ltd., specific surface area 200 m ² / g, average pore radius; 5 nm, pore volume;
0.48 ml / g, average particle size; 50 μm] was used.
As an organic emulsion, acrylic emulsion [trade name: Boncoat 36 manufactured by Dainippon Ink and Chemicals, Inc.
25, glass transition temperature is -43 ° C, emulsion particle size;
0.25 μm, active ingredient 59.5 wt%] was used.

[0028]

[Table 1]

Table 1 shows the composition table of the humidity control sheet A. The above blends were added to a kneader along with the respective blending ratios and kneaded to obtain a coating agent A. The coating was carried out with a comma coater so that the thickness of the coating layer after drying was 500 μm, and a humidity control sheet A was produced as a trial.

Example 2 Inorganic porous material was prepared by adding activated clay (trade name: Galleon Earth manufactured by Mizusawa Chemical Industry Co., Ltd., specific surface area 320 m ² / g, average pore radius: 3 nm, pore volume: 0.45 ml /). g, average particle diameter; 50 μm] was used. The organic emulsion is
The acrylic emulsion of Example 1 was used.

[0031]

[Table 2]

Table 2 shows the composition table of the humidity control sheet B. The above blends were added to a kneading machine along the respective blending ratios and kneaded to obtain a coating agent B. The coating was carried out using a comma coater so that the thickness of the coating layer after drying was 500 μm, and a humidity control sheet B was produced as a trial.

Example 3 Inorganic porous material was prepared by adding pseudoboehmite [trade name: Alumina G-250 manufactured by Alcoa Co., specific surface area 350 m ² / g, average pore radius; 3.5 nm, pore volume; 6 ml / g, average particle size; 50 μm] was used. The organic emulsion is
The acrylic emulsion of Example 1 was used.

[0034]

[Table 3]

Table 3 shows the composition table of the humidity control sheet C. The above blends were added to a kneader along with the respective blending ratios and kneaded to obtain a coating agent C. The coating was carried out using a comma coater so that the thickness of the coating layer after drying was 500 μm, and a humidity control sheet C was produced as a trial.

Comparative Example 1 As an organic emulsion, ethylene vinyl acetate emulsion [Rika Bond BE manufactured by Chuo Rika Kogyo Co., Ltd.
-920, glass transition temperature 0 ℃, particle size of emulsion;
0.7 μm, active ingredient 60 wt%] was used. The activated alumina of Example 1 was used as the inorganic porous body.

[0037]

[Table 4]

Table 4 shows the composition table of the humidity control sheet D. The above blends were added to the kneader along with the respective blending ratios and kneaded to obtain a coating agent D. The coating was carried out using a comma coater so that the thickness of the coating layer after drying was 500 μm, and a humidity control sheet D was produced as a trial.

Comparative Example 2 Inorganic porous material was prepared by adding diatomaceous earth [Radiolite # 2000 manufactured by Showa Chemical Industry Co., Ltd., specific surface area 1 m ² / g, average pore radius; 90 nm, pore volume; 0.0005 ml]. / G, average particle diameter; 20 μm] was used. The acrylic emulsion of Example 1 was used as the organic emulsion.

[0040]

[Table 5]

Table 5 shows the composition table of the humidity control sheet E. The above blends were added to a kneading machine along with the respective blending ratios and kneaded to obtain a coating agent E. The coating was carried out with a comma coater so that the thickness of the coating layer after drying was 500 μm, and a humidity control sheet E was produced as a trial.

Table 6 shows the volume of pores having an average pore diameter of 3 to 12 nm in the inorganic porous materials used in Examples 1, 2, 3 and Comparative Example 2.

[0043]

[Table 6]

Comparative Example 2 A commercially available vinyl cloth was used for comparison.

[Evaluation Method] (1) Evaluation of Appearance of Film Forming State The presence or absence of cracks in the coating layer was visually evaluated. ◯ (no crack), Δ (partially cracked), × (large number of cracks) (2) Folding resistance The sheet was bent 180 degrees, and the appearance of the bent portion was visually evaluated. ○ (No crack), △ (Partially cracked), × (Whole surface cracked) (3) Method for measuring humidity control property A predetermined area of the sample is exposed in a closed space of a specified volume, and temperature fluctuations occur in the closed space from the outside. Humidity control characteristics were determined from temperature and humidity changes and relative humidity changes when given. When the humidity control function does not work, the relative humidity greatly fluctuates depending on the temperature fluctuation, but when the humidity control function works, the fluctuation of the relative humidity is suppressed. The degree of suppression of this fluctuation was determined by the difference between the highest humidity and the lowest humidity measured in space, and the humidity control characteristics were evaluated. (4) Method of measuring moisture absorption / desorption characteristics First, a measurement sample was measured at 25 ° C and 50% R.V. H. Equilibrate in a constant temperature and humidity bath. Then sample at 25 ℃, 90%
R. H. It is placed in a constant temperature and constant humidity tank, and the amount of moisture absorption is measured for 24 hours. Then, again, at 25 ° C. and 50% R.
H. Put it in the constant temperature and humidity chamber and measure the amount of moisture released.

[Experimental Results] Appearance evaluation result of film formation Table 7 shows the evaluation results.

[0047]

[Table 7]

As is clear from Table 7, in Examples 1, 2 and 3 in which the acrylic emulsion [trade name: Boncoat 3625 manufactured by Dainippon Ink and Chemicals, Inc.] was blended, no crack was observed, but ethylene was used. A large number of cracks were generated in Comparative Example 1 containing a vinyl acetate emulsion [manufactured by Chuo Rika Kogyo Co., Ltd.]. Since the acrylic emulsion has a very high plasticity, it has excellent crack resistance even when the film thickness is as thick as 500 μm. In Comparative Example 2, some cracks occurred. This is because the blended diatomaceous earth has a particle size of Example 1,
This is because, compared to a few inorganic porous materials such as activated alumina, the shape is finer and flat, so that the filling property inside the coating is poor and the shrinkage is very large.

Evaluation result of bending resistance Table 8 shows the evaluation results.

[0050]

[Table 8]

An acrylic porous emulsion [trade name: Boncoat 3625 manufactured by Dainippon Ink and Chemicals, Inc.] having excellent plasticity as well as crack resistance is blended to form an inorganic porous material having a particle diameter of about 50 μm and a nearly spherical shape. Examples 1, 2, 3 used
Indicates that the bending resistance is superior to Comparative Examples 1 and 2.

Measurement results of humidity control characteristics Table 9 shows the measurement results.

[0053]

[Table 9]

As is clear from Table 9, the volume of pores having an average pore diameter of 3 to 12 nm such as activated alumina is 0.3 ml.
In Examples 1, 2, and 3 in which the inorganic porous material (Table 6) having a weight ratio of 1 / g or more is mixed, the relative humidity fluctuation is significantly suppressed,
Compared with Comparative Example 2 and vinyl cloth containing a small diatomaceous earth having an average pore diameter of 3 to 12 nm and a small pore volume, excellent humidity control characteristics are shown. It should be noted that Comparative Example 1 shows excellent humidity control characteristics because active alumina is mixed in the humidity control characteristics although cracks are generated.

Measurement results of moisture absorption and desorption characteristics Table 10 shows the measurement results.

[0056]

[Table 10]

Similar to the humidity control property, Examples 1, 2 and 3 in which an inorganic porous material such as activated alumina having a volume of pores having an average pore diameter of 3 to 12 nm is 0.3 ml / g or more are blended,
Compared to Comparative Example 2 and vinyl cloth containing a small diatomaceous earth having an average pore diameter of 3 to 12 nm, it shows excellent moisture absorption and desorption characteristics, and even when the high humidity condition continues for a long time like the rainy season. The moisture absorption capacity can be maintained and no condensation will occur.

Comparative Example 3 As an emulsion of an organic substance, a fluorine emulsion [Lumiflon emulsion FE43 manufactured by Asahi Glass Co., Ltd.
00, average particle size of emulsion; 0.15 μm, active ingredient 50 wt%]. The activated alumina of Example 1 was used as the inorganic porous body.

[0059]

[Table 11]

Table 11 shows a composition table of the humidity control sheet F. Add the above composition to the kneading machine according to the respective composition ratio,
The mixture was kneaded to obtain a coating agent F. The coating was carried out with a comma coater so that the thickness of the coating layer after drying was 500 μm, and a humidity control sheet F was produced as a trial.

Comparative Example 4 A solvent-based acrylic coating agent [trade name: Almatex L-1060 manufactured by Mitsui Chemicals, Inc., glass transition temperature: 25 ° C., active ingredient 40 wt%] was used in place of the acrylic emulsion of the organic substance emulsion. I was there. The activated alumina of Example 1 was used as the inorganic porous body.

[0062]

[Table 12]

Table 12 shows a composition table of the humidity control sheet G. Add the above composition to the kneading machine according to the respective composition ratio,
The mixture was kneaded to obtain coating agent G. The coating was carried out using a comma coater so that the thickness of the coating layer after drying was 500 μm, and a sheet G was manufactured as a prototype.

Comparative Example 5 Instead of the fluorine emulsion, a solvent type fluorine coating agent [Lumiflon LF20 under the trade name of Asahi Glass Co., Ltd.]
0, 60 wt% active ingredient] was used. The inorganic porous material is
The activated alumina of Example 1 was used.

[0065]

[Table 13]

Table 13 shows a composition table of the humidity control sheet H. Add the above composition to the kneading machine according to the respective composition ratio,
The mixture was kneaded to obtain coating agent H. The coating was carried out using a comma coater so that the thickness of the coating layer after drying was 500 μm, and a sheet H was manufactured as a trial.

Comparative Example 6 A coating film was formed on a wall paper having a basis weight of 65 g so that the acrylic emulsion used in Example 1 alone was dried by a bar coater to a thickness of 50 μm and dried at room temperature for 24 hours. Then, a sheet I was obtained.

The results of evaluation of bending resistance, moisture absorption / release characteristics and water repellency of Example 1 and Comparative Examples 3, 4, 5, and 6 are shown below. A CA-X type contact angle measuring instrument manufactured by Kyowa Interface Science Co., Ltd. is used for the evaluation of water repellency, and the measurement conditions are water drops in the air (25 ° C.) and pure water (10 μl).

[0069]

[Table 14]

As is clear from Table 14, Example 1 in which an acrylic emulsion and fluorine emulsion were respectively mixed, Comparative Examples 4 and 6 in which a solvent type acrylic coating agent and a solvent type fluorine coating agent were respectively mixed. Better in bending resistance than No. 5.

Measurement results of humidity control characteristics Table 15 shows the measurement results.

[0072]

[Table 15]

As is clear from Table 15, Example 1 and Comparative Example 3 in which the acrylic emulsion and the fluorine emulsion were respectively mixed were Comparative Examples 4 and 5 in which the solvent-based acrylic coating agent and the solvent-based fluorine coating agent were respectively blended. In comparison, it exhibits excellent moisture absorption and desorption.

Water repellency evaluation result Table 16 shows the measurement results.

[0075]

[Table 16]

As is clear from Table 16, Example 1 and Comparative Example 3 in which the emulsion of the organic material and the inorganic porous material were blended
Shows super water repellency, but Comparative Example 4 using a solvent-based acrylic coating agent and a solvent-based fluorine coating agent
No. 5 has not reached the point of exhibiting super water repellency. In addition, Comparative Example 6 coated with only an acrylic emulsion does not show high water repellency.

[0077]

EFFECTS OF THE INVENTION According to the present invention, it has an excellent moisture absorbing / releasing function, good flexibility, and a superhydrophobic surface.
It becomes possible to provide a functional sheet with excellent workability.

[Brief description of drawings]

FIG. 1 is an SEM observation image of the surface and cross section of a cured coating film of a mixture containing an inorganic porous material and an organic emulsion of Example 1.

FIG. 2 is a diagram showing a structural model of a cured film of a mixture containing an inorganic porous material and an organic emulsion, which is estimated by SEM observation or the like.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Eiko Ohashi             2-1-1 Nakajima, Kokurakita-ku, Kitakyushu City, Fukuoka Prefecture             No. Totoki Equipment Co., Ltd. (72) Inventor Makoto Nakanishi             2-1-1 Nakajima, Kokurakita-ku, Kitakyushu City, Fukuoka Prefecture             No. Totoki Equipment Co., Ltd. F term (reference) 2E001 DB03 FA03 FA11 FA14 GA24                       GA27 GA28 HC07 HD11 JA06                       JA22 JB07 LA04                 4F100 AA00B AA19 AK01B AK25                       AT00A BA02 BA03 BA07                       BA10A BA10C DE01B DE01C                       DG10 DJ00B EH46 EJ40                       EJ86 GB07 JA05B JA06B                       JA20B JD04 JD15 JK13                       JK13A JK17 JK17A JL01                       JL07 JL08C JM01 JM01B                       YY00B

Claims (11)

[Claims] 1. A flexible base material having a pore diameter of 3 to 12 nm and a pore volume of 0.3 ml on the surface thereof.
/ G or more of inorganic porous material and glass transition temperature of -30 to 30
A functional sheet, which is coated with a dried product of a mixture containing an organic emulsion at −50 ° C. 2. The content of the inorganic porous material in the mixture is
2 per 100 parts by weight dry weight of organic emulsion
The functional sheet according to claim 1, wherein the functional sheet is 100 to 400 parts by weight. 3. The coating layer of the dried product of the mixture is 300 μm.
The functional sheet according to claim 1 or 2, which has a film thickness of m or more. 4. The average particle size of the inorganic porous material is 30 μm.
It is -60 micrometers, The functional sheet of Claims 1-3 characterized by the above-mentioned. 5. The coating agent for coating the surface of the substrate with the mixture of the inorganic porous material and the emulsion of an organic substance contains 20 to 40 parts by weight of water per 100 parts by weight and has a viscosity of 4000 to 5000 mPa. The functional sheet according to any one of claims 1 to 4, characterized in that 6. The particle size of particles in the organic emulsion is smaller than the particle size of the inorganic porous material, and has an average particle size of 0.2 μm or more.
Functional sheet described in. 7. The functional sheet according to claim 1, wherein the inorganic porous material is substantially spherical particles. 8. A pattern processing is performed by a method of pressing a roll having a three-dimensional pattern on the coating layer of the mixture of the functional sheet according to claim 1 or 2. Functional sheet. 9. A step of applying the mixture onto the surface of the flexible base material and a step of drying the applied film until the applied film is in a semi-dried state are carried out in this order, 9. The functional sheet according to claim 8, wherein a step of patterning is performed by a method of pressing a roll having a three-dimensional pattern on the surface of the coating, and then the coating is completely dried. 10. A functional sheet comprising photocatalyst particles further carried on the coating layer of the mixture of the functional sheets according to claim 1. 11. A step of applying the mixture onto the surface of the flexible substrate and a step of drying the applied film until the applied film is in a semi-dried state are carried out in this order, The functional sheet according to claim 10, wherein the surface of the coating is coated with photocatalyst particles, and then the coating is completely dried.