JPH11314308A - Laminate having inorganic porous crystal-hydrophilic polymeric composite layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminate having a layer comprising an inorganic. porous crystal-hydrophilic polymeric composite wherein inorganic. porous crystals are contained in a hydrophilic polymer and a base material enhancing functions. SOLUTION: A laminate is obtained by laminating a layer comprising an inorganic porous crystal-hydrophilic polymeric composite wherein inorganic porous crystals are contained in a hydrophilic polymer on a function-enhancing base material and useful as a material having high strength, improved such as or the like functionality in addition to the gas absorbing capacity, volatile organic solvent removing capacity, fire retardancy, heat insulating properties and heavy metal/radioactive element removing capacity possessed by the organic porous crystal-hydrophilic polymeric composite. Further, by supporting a metal on inorg. porous crystals, a laminate to which antibacterial and malodor removing properties are further imparted can be provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic polymer having properties such as offensive odor removal and gas adsorption, as well as antibacterial properties, flame retardancy, heat retention, etc., and excellent strength and other properties. The present invention relates to a laminate comprising a layer composed of an inorganic porous crystal-hydrophilic polymer composite having an inorganic porous crystal in its body and a functional improving substrate.

[0002]

2. Description of the Related Art There is known a material in which an inorganic compound such as zeolite or alumino-silica gel is supported on a hydrophilic polymer such as a cellulose substrate such as paper to impart functionality. Such a material has properties such as offensive odor removal and gas adsorption, antibacterial properties, flame retardancy, and heat retention, so that it can be used for various applications.

[0003]

The above-mentioned materials can be expected to be used in various applications. However, depending on the applications actually demanded by consumers, materials having higher functions such as higher strength are required. I have. An object of the present invention is to provide a material that meets such demands, wherein the hydrophilic polymer has an inorganic porous crystal having an inorganic porous crystal in its body. Another object of the present invention is to provide a product having enhanced functionality in addition to antibacterial properties, flame retardancy, and heat retention.

[0004]

This object is solved by the present invention described below. That is, the present invention is as follows. (1) A laminate characterized in that a hydrophilic polymer has a layer composed of an inorganic porous crystal-hydrophilic polymer composite having an inorganic porous crystal in the substance and a function-improving substrate. (2) The function-improving substrate is selected from the group consisting of plastic films, regenerated cellulose films, metal foils, natural fibers, semi-synthetic fibers, synthetic fibers, metal fibers, inorganic fibers, activated carbon fibers, inorganic hardeners, and inorganic films. The laminate according to the above (1), comprising at least one kind. (3) When the hydrophilic polymer is natural cellulose, regenerated cellulose, bacterial cellulose, chemically modified cellulose, silk,
The laminate according to the above (1), comprising at least one selected from the group consisting of wool, polyacrylamide, polyvinyl alcohol, crosslinked polyvinyl alcohol, chitin, chitosan, ethylene vinyl acetate copolymer and polyvinyl formal. (4) The laminate according to (3), wherein the natural cellulose is at least one selected from the group consisting of pulp, cotton, hemp, and kenaf. (5) The laminate according to (3), wherein the chemically modified cellulose is at least one selected from the group consisting of ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl hydroxyethyl cellulose, and carboxymethyl cellulose. (6) The laminate according to the above (1), wherein the inorganic porous crystal is zeolite. (7) The laminate according to the above (1), wherein the inorganic porous crystal supports at least one metal selected from the group consisting of silver, copper, zinc, iron, nickel, cobalt, palladium and platinum.

The function-improving base material used in the present invention has a moderate strength (for example, a strength measured by JIS P8113 “Testing method for tensile strength of paper and paperboard” of 300).
About 1000 gf, preferably about 500 to 750 gf, or a strength of about 4 to 1500 gf / d measured according to JIS L1069 "Testing method for tensile strength of fiber".
(Preferably about 20 to 500 gf / d), and other properties that are not included in the layer made of the inorganic porous crystal-hydrophilic polymer composite or that the layer has, such as texture, weather resistance, and water resistance. And those having heat retention, electromagnetic wave resistance and the like. Specifically, for example, wool,
Natural fibers such as silk, cotton, hemp, semi-synthetic fibers such as rayon and cupra, polyethylene terephthalate polyester fibers, polyolefin fibers, polyurethane fibers, (poly)
Knitted fabrics, woven fabrics and non-woven fabrics made from at least one fiber selected from synthetic fibers such as acrylic fibers, metal fibers such as copper, aluminum and iron, glass fibers, inorganic fibers such as carbon fibers, and activated carbon fibers by a method known per se. And the like. The above synthetic fiber may be a copolymer, and the natural fiber and the inorganic fiber may be a blend. The fineness of the constituent fibers, the cross-sectional shape, the presence or absence of various polymer stabilizers, the basis weight, the density, and the like in the sheet-like material are not particularly limited. The thickness of the function-improving base material made of these sheet-like materials is about 1 to 500 μm, and preferably 10 to 100 μm.

[0006] In addition to the above-mentioned fiber sheet material, a plastic film or sheet made of a material such as polyurethane, polyester, polyolefin, polyvinyl chloride, polyvinyl alcohol or polyacrylamide (hereinafter referred to as a functional improving substrate used in the present invention). , "Plastic film"), regenerated cellulose film or sheet such as cellophane, metal foil made of copper, iron, aluminum, stainless steel, etc., board or sheet made of inorganic hardener made of cement, gypsum, etc., titanium dioxide And an inorganic film made of glass or the like.

[0007] Silk, rayon, cotton, hemp, and kenaf are preferable as the texture-improving base material when desired, and polyolefins such as polyethylene, polypropylene, polystyrene, and polyethylene terephthalate when weather and water resistance are desired. -Based resin, aramid resin, film or sheet made of polyacrylate-based resin or fiber, or inorganic film such as titanium dioxide, glass, etc. If heat insulation is desired, wool, polyacrylonitrile fiber, aluminum foil, foamed polyurethane It is preferable to use expanded polystyrene, and when electromagnetic wave resistance is desired, it is preferable to use metal fibers or metal foils such as iron, aluminum, and copper.

The plastic film may be stretched or unstretched, but is preferably stretched from the viewpoint of strength, and the stretching method and stretching ratio are not particularly limited.
In addition, the plastic film may be in the form of a foamed plastic film from the viewpoint of improving heat retention and buffering properties. The method of manufacturing a foamed plastic film is to mix a gas or a gasizable liquid under pressure with a thermoplastic, heat it, return it to normal pressure, etc. to make it foam, or mix a decomposable foaming agent. In addition, a method of foaming by heating decomposition, a method of foaming using a gas generated during the polymerization reaction, and the like can be given. The expansion ratio is not particularly limited. Examples of the foamed plastic include foamed polystyrene and foamed polyurethane. The thickness of the plastic film is about 10 to 500 μm, preferably 20 to 100 μm.

[0009] Examples of the regenerated cellulose film include cellophane. The thickness of the regenerated cellulose film is about 10 to 500 μm, preferably 20
１００100 μm.

The shape of the metal foil is not particularly limited.
It is preferable that the mesh is formed in view of cost, weight, performance and the like. As a method of forming the metal foil into a net-like structure, for example, a method of punching or temporarily processing into a fibrous shape and then forming it into a net shape may be mentioned. Metal foil thickness is 10 ~ 200μ
m, preferably 20 to 100 μm.

Examples of the inorganic hardener include cement, gypsum, plaster, mortar, calcium silicate and the like. When an inorganic curing agent is used as the function-improving base material, its thickness is 0.5 to 20 cm, preferably 1 to 20 cm.
〜１０10 cm.

Examples of the inorganic film include glass, ceramics, titanium dioxide, zeolite and the like. The thickness of the inorganic film is 5 to 100 μm, preferably 10 to 100 μm.
50 μm.

The function-improving base material used in the present invention is selected from the above-mentioned sheet materials such as knits, woven fabrics and nonwoven fabrics, plastic films, regenerated cellulose films, metal foils, inorganic hardener boards and sheets, and inorganic films. At least one of them. As a method for producing a functional enhancement substrate containing two different materials, for example, a functional enhancement substrate is produced from a polyethylene film and a metal foil, or a sheet material such as a knitted fabric, a woven fabric and a nonwoven fabric, and a thermoplastic resin. In such a case, a method in which two different kinds of materials are stacked and then heat-sealed through a hot roll may be used. Further, there is a method of providing an adhesive layer on a board made of gypsum and affixing a polyurethane foam thereon.

The inorganic porous crystal of the inorganic porous crystal-hydrophilic polymer composite used in the present invention includes an inorganic ion exchanger crystal having an ion exchange ability and an adsorbent crystal having an adsorption ability in a porous portion. There is no particular limitation as long as it does not dissolve, decompose, or disintegrate the hydrophilic polymer. Examples include zeolite, hydrotalcite, hydroxyapatite, clay minerals and the like. Among them, most applications zeolite preferably terms is wide, 4A zeolite terms relatively synthesized Among them is easy _{[Na 12 Si 12 Al 12 O 48} · 27H 2 O ] is particularly preferred.

The hydrophilic polymer of the inorganic porous crystal-hydrophilic polymer composite used in the present invention is not particularly limited as long as it swells in water. For example, natural cellulose (pulp, kenaf, cotton, hemp), regenerated cellulose (cellophane, cellulose beads, rayon, cellulose sponge, etc.), cotton, bacterial cellulose and ethyl cellulose chemically modified with cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, Cellulose derivatives such as ethyl hydroxyethyl cellulose and carboxymethyl cellulose,
Further, natural or artificial hydrophilic polymers such as silk, wool, hemp, polyvinyl alcohol, cross-linked polyvinyl alcohol, chitin, chitosan, ethylene vinyl acetate copolymer, polyvinyl formal, and superabsorbent polymer gels such as polyacrylamide; Collagen, propolis, lacquer, wood flour and the like can be mentioned. Above all, pulp and regenerated cellulose are preferably used in terms of actual use form, price, and ease of handling.

An inorganic porous crystal is supported in the body of the above hydrophilic polymer to form an inorganic porous crystal-hydrophilic polymer composite used in the present invention. Here, the entity of the hydrophilic polymer is, for example, when the hydrophilic polymer is cellulose,
It means the inside of a substrate containing cellulose as a component, and does not include, for example, the cell wall surface of cellulose, pores existing in the cell wall, and cell lumen (lumen). Having inorganic porous crystals in the body of the cellulose substrate means that some or all of the inorganic porous crystals are present in the body of the cellulose substrate.

The inorganic porous crystal-hydrophilic polymer composite is produced as follows. For example, when the inorganic porous crystal is a zeolite and the hydrophilic polymer is a zeolite-cellulose composite in which the hydrophilic polymer is cellulose, Japanese Patent Application No. Hei.
No. 45538 (specifically, from 1.0 to 100).
A cellulose substrate impregnated with an aqueous solution of a silicon compound at a concentration of 1.0 mmol / l for 10 minutes to 2 hours at 1.0 to 200 ° C.
1000 mmol / l aluminum compound and 10
2 to a mixed aqueous solution of ~ 5000 mmol / l basic substance
For 20 hours to 20 days. When the hydrophilic polymer is pulp, cellophane or rayon, an inorganic porous crystal-pulp composite, an inorganic porous crystal-cellophane composite, or an inorganic porous crystal-rayon composite can be obtained in the same manner as described above. Inorganic porous crystal
The ratio of the inorganic porous crystal in the hydrophilic polymer composite is not particularly limited, but is preferably 1.0 to 70.0% by weight, particularly preferably 10.0 to 50.0% by weight.

FIGS. 1 and 2 show a preferred embodiment of the laminate of the present invention when the inorganic porous crystal-hydrophilic polymer composite is an inorganic porous crystal-supported pulp composite. In FIG. 1, reference numeral 1 denotes a function improving base material, which is an aggregate of fibrous materials. Reference numeral 2 denotes a layer made of an inorganic porous crystal-hydrophilic polymer composite, in which the hydrophilic polymer is an aggregate of fibrous materials. FIG.
In the above, 1 ′ is a function-improving substrate, which is in the form of a film. Reference numeral 2 denotes a layer made of an inorganic porous crystal-hydrophilic polymer composite, in which the hydrophilic polymer is an aggregate of fibrous materials. FIG.
And the laminate shown in FIG. 2 can be mainly used for applications such as freshness retaining cardboard, rustproof cardboard, insect-proof cardboard, flame-resistant cardboard liner, shoji paper, bran paper, wallpaper, curtains, carpets, carpets, tapestries, etc. it can.

The layer composed of the inorganic porous crystal-hydrophilic polymer composite can take various shapes depending on the kind of the hydrophilic polymer. For example, when the hydrophilic polymer is polyvinyl alcohol, cross-linked polyvinyl alcohol, or the like,
It can take the form of a film. FIG. 3 shows a preferred embodiment of the laminate of the present invention when the layer composed of the inorganic porous crystal-hydrophilic polymer composite is in the form of a film. In FIG. 3, reference numeral 1 'denotes a function-improving substrate, which is in the form of a film. 2 'is a layer composed of an inorganic porous crystal-hydrophilic polymer composite, and in the example of FIG. 3, the hydrophilic polymer is in a film form. The laminate shown in FIG. 3 can be mainly used for applications such as a freshness retaining sheet, a rust-proof sheet, and an insect-proof sheet. Inorganic porous crystal in the form of a film
The thickness of the layer composed of the hydrophilic polymer composite is 10 to 500.
It is about μm, preferably 20 to 100 μm.

In the example shown in FIG. 4, 2 ″ is an inorganic porous crystal.
The layer is made of a hydrophilic polymer composite, has a cylindrical shape, and has a through hole in its longitudinal direction. Reference numeral 1 denotes a function improving base material, which is filled in the through holes. In the embodiment of FIG. 4, the hydrophilic polymer is, for example, a regenerated cellulose substrate such as rayon, and the function-improving substrate is an aggregate of fibrous materials. In this embodiment, a regenerated cellulose such as rayon is preferable as the hydrophilic polymer, and a plastic or natural fiber, metal fiber, glass fiber, or the like made of a material such as polyolefin is used as the function improving substrate 1.
A sheet-like material such as a knitted fabric, a woven fabric, and a nonwoven fabric made of at least one kind of fiber selected from inorganic fibers such as carbon fiber is preferable. The laminate can be mainly used for applications such as an air conditioner filter, a vacuum cleaner garbage pack, a tropical fish tank filter, and a drainage filter. The shape of the cross section in the center direction of the through hole is a perfect circle, an ellipse, a quadrangle, etc., and in the case of a perfect circle, its diameter is about 1 to 100 μm,
In the case of an ellipse, the length of the long axis is about ^{2 to} 100 μm, and the length of the short axis is about 1 to 50 μm. When necessary, the cross-sectional area is usually 0.79 to 7900 μm ² , preferably 2000 μm ² . . The length of the composite in the longitudinal direction is about 1 to 200 μm, and the length in the width direction is 5 to 1000 μm
It is about.

FIG. 5 shows a laminate obtained by further laminating the laminate shown in FIG. 3 on the laminate shown in FIG. As the function-improving substrate 1, a nonwoven fabric made of natural fibers is suitable.
As the layer 2 composed of the inorganic porous crystal-hydrophilic polymer composite, a zeolite-pulp composite layer is preferable. A plastic film, particularly a copolymerized polyvinyl alcohol film, is suitable as the function improving substrate 1 ', and a zeolite-cellophane composite layer is suitable as the layer 2' composed of an inorganic porous crystal-hydrophilic polymer composite. If the thickness of the composite laminate exceeds 500 μm, it tends to be unfavorable in terms of moldability into a box shape or a honeycomb shape, or portability. The laminate shown in FIG. 5 can be mainly used for applications such as a portable toilet for a car, a disposable diaper, and a water purifier for survival.

The layer composed of the inorganic porous crystal-hydrophilic polymer composite may be further enhanced by adding a volatile substance in addition to the inorganic porous crystal-hydrophilic polymer composite. Examples of the volatile substances include L-menthol, hinokitiol, phytontide, wasabiol,
Limonene and the like. These can be supported by a method known per se, for example, impregnation, coating, press-fitting and the like.

By immersing the inorganic porous crystal-hydrophilic polymer composite in an aqueous solution of a metal salt having a catalytic function, a metal-supported inorganic porous crystal-hydrophilic polymer composite can be obtained. Examples of the metal used include silver, copper, zinc, iron, nickel, cobalt, palladium, platinum, and the like, and a plurality of these metals may be used in combination. The concentration of the aqueous solution of the metal salt is not particularly limited, but is preferably 1.
It is 0 to 100 mmol / l, and there is no particular limitation on the temperature and time for immersion. At this time, since the hydrophilic polymer can permeate the aqueous solution, the metal can be supported on the entire inorganic porous crystal in the body of the hydrophilic polymer without waste. The amount of metal in the metal-supported inorganic porous crystal-hydrophilic polymer composite is not particularly limited, but is preferably 0.001 to 10.0% by weight, and more preferably 0.01 to 1.0% by weight.

For example, an inorganic porous crystal-hydrophilic polymer composite supporting silver, copper or zinc exhibits antibacterial properties, and an inorganic porous crystal-hydrophilic polymer composite supporting palladium or platinum contains ethylene. Since it can be adsorbed, it has the effect of maintaining the freshness of fruits and vegetables, and the inorganic porous crystal-hydrophilic polymer composite carrying silver or copper can adsorb and decompose hydrogen sulfide, and thus has the rust-preventive effect of metals or It has a deodorizing effect and has an anti-odor effect because it can adsorb and decompose ammonia. In addition, the inorganic porous crystal-hydrophilic polymer composite carrying silver can adsorb and decompose methyl mercaptan, and thus has an odor preventing effect. At this time, since the hydrophilic polymer can sufficiently permeate the gas, the entirety of the metal-supported inorganic porous crystal in the entity of the hydrophilic polymer is used without waste,
Gas can be adsorbed and decomposed.

The laminate of the present invention is manufactured by the following method. When the function-improving base material is the above-mentioned sheet-like material and the hydrophilic polymer of the inorganic porous crystal-hydrophilic polymer composite is pulp, the base material and the inorganic porous crystal-hydrophilic polymer composite are used. To obtain a laminate. When the function-improving substrate is other than the above sheet-like material, a method of attaching a layer composed of an inorganic porous crystal-hydrophilic polymer composite to at least one surface of the substrate with an adhesive or the like, or cement or gypsum or the like A laminate is obtained by a method in which a layer made of an inorganic porous crystal-hydrophilic polymer composite is attached with an adhesive or the like before the inorganic hardening agent is completely solidified. The thickness of the adhesive layer is about 5 to 100 μm, preferably 10 to 50 μm.

In the embodiment in which the inorganic porous crystal-hydrophilic polymer composite has a through hole in the longitudinal direction, a method of filling the through hole with the function-enhancing base material or a screw around the function-enhancing base material is used. It is manufactured by a method of passing a regeneration bath with the course attached.

The laminate of the present invention may be, for example, a knitted fabric made of a natural fiber having hydrophilicity and gas permeability, in addition to a layer comprising a functional enhancement substrate and an inorganic porous crystal-hydrophilic polymer composite. A sheet-like material such as a woven fabric and a non-woven fabric, a functional film-improving base material such as a plastic film or a mesh-like metal foil can be further laminated. The thickness of the substrate is similar to that described above.

The laminate of the present invention is obtained by laminating a layer comprising an inorganic porous crystal-hydrophilic polymer composite in which a hydrophilic polymer has an inorganic porous crystal in its body on a function-improving substrate. -In addition to the gas adsorption ability, volatile organic solvent removal ability, flame retardancy, heat retention, heavy metal and radioactive element removal ability of the hydrophilic polymer complex, it has high strength,
Furthermore, it can improve the tactile sensation such as touch, hydrophilicity, water repellency, and rust prevention. For example, underwear, foot mats, sheets, gloves, pillowcases, batting, sash, etc. Paper, wallpaper, costume cover, cushion cover, futon storage bag, insect repellent sheet, vacuum cleaner pack, air conditioner filter, air purifier filter, tableware bundle, drainer garbage bag, carpet, hot carpet cover, curtain, refrigerator deodorization Sheet, special filter paper,
It can be used for various purposes such as freshness preserving sheets for vegetables and meats, packaging materials for freshness preserving and transporting, wall materials, flooring materials, ceiling materials, dew condensation water absorbing sheets and the like.

In particular, a metal-supported inorganic porous crystal-hydrophilic polymer composite in which a metal such as silver, copper, or zinc is supported on the inorganic porous crystal-hydrophilic polymer composite used in the laminate of the present invention is used. Thereby, in addition to the above properties, properties such as antibacterial property and odor removing ability can be further provided. Therefore, it can also be used for various purposes such as disposable diapers, diaper covers, portable toilets for automobiles, insoles, artificial leather, interiors (seat seats, seat covers) of automobiles, trains, airplanes and ships, towels, toilet seat covers, etc. Can be.

[0030]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Production Example 1 After 300 g of pulp was impregnated with an aqueous solution of sodium metasilicate nonahydrate (190 g / 5000 ml), 150 g of sodium aluminate and sodium hydroxide 3
Zeolite-supported pulp was obtained by adding 30 g of a mixed aqueous solution 5000 ml and immersing the mixture at 90 ° C. for 2 hours. The zeolite carrying ratio of the obtained zeolite carrying pulp was 30.1% by weight. This zeolite-supporting pulp is subjected to an inclined wire mesh type paper machine (inclination angle 5 °, speed 10 m / min)
Was used to prepare a zeolite-supporting paper having a basis weight of 100 g / m ² and a paper width of 50 cm.

Example 1 A laminate obtained by laminating a rayon nonwoven fabric (basis weight: 60 g / m ² , cloth width: 50 cm) manufactured by a wet method using starch paste as a binder on the zeolite-supporting paper obtained in Production Example 1. I got

Example 2 The zeolite-carrying paper obtained in Production Example 1 was passed through a hot roll and heated to a surface temperature of 150 ° C. A laminate was obtained by continuously contacting a nonwoven fabric (thickness: 30 μm) made of a polyethylene-polypropylene conjugate fiber produced by a dry method while spraying the polymer-absorbing polymer powder on the mixture.

Example 3 The zeolite-supporting paper obtained in Production Example 1 was passed through a hot roll and heated to a surface temperature of 150 ° C. This operation is made in two systems, and the thickness of this paper is 40 μm and the width is 50 c.
m of low density polyethylene (LDPE) film were continuously contacted. As a result, a laminate was obtained in which the LDPE film was sandwiched between the carrier papers by heat fusion.

Example 4 The zeolite-carrying paper obtained in Production Example 1 was passed through a hot roll and heated to a surface temperature of 150 ° C. This operation was performed in two systems, and a polyethylene nonwoven fabric (thickness: 30 μm) manufactured by a dry method was continuously contacted between the papers. As a result, a laminate in which the polyethylene nonwoven fabric was sandwiched between the carrier papers by heat fusion was obtained.

Production Example 2 After impregnating 200 g of cellophane in an aqueous solution of sodium metasilicate 9-hydrate (190 g / 5000 ml),
It was impregnated with 5000 ml of a mixed aqueous solution of 150 g of sodium aluminate and 330 g of sodium hydroxide. Thereafter, the reaction was carried out for 4 hours in a steam generator in which steam at 110 ° C. was generated, to obtain cellophane supporting zeolite. The obtained cellophane-supported cellophane had a zeolite loading of 15.3% by weight.

Example 5 The cellophane supporting zeolite obtained in Production Example 2 was passed through a hot roll and heated to a surface temperature of 150 ° C. This operation is made in two lines, and the thickness of this cellophane is 40μ.
m, an LDPE film having a width of 50 cm was continuously brought into contact. Thus, a laminated body sandwiched by the heat-sealing of the LDPE film between the supported cellophane was obtained.

Example 6 15.0 g of the laminate obtained in Example 5 was immersed in 500 ml of an aqueous solution of 2.20 g of copper sulfate pentahydrate for 2 hours. Thus, a laminate in which 5.0 mmol of copper was supported on the laminate was obtained.

Example 7 High-strength rayon fiber (polypropylene diameter: 20 μm; fineness: 50 μm; average fiber length: 20 mm) in which polypropylene was inserted into the core of the rayon during the regeneration of the rayon
100 g of sodium metasilicate 9-hydrate was impregnated with an aqueous solution (85 g / 2000 ml), and then a mixed aqueous solution of 80 g of sodium aluminate and 160 g of sodium hydroxide (2000 ml) was added. Thus, a zeolite-supported rayon, which is one embodiment of the laminate shown by No. 4, was obtained. The zeolite-carrying rayon has high strength, and zeolite is generated only in the rayon portion. The zeolite carrying ratio of this zeolite carrying rayon was 23.5% by weight.

Example 8 A nonwoven fabric produced by a wet method from the zeolite-supported rayon obtained in Example 7 and a polyethylene nonwoven fabric produced by a dry method were subjected to a heat treatment in the same manner as in Example 3, followed by contact and fusion. Thereafter, a sheet made of activated carbon fiber manufactured by a dry method was contacted and fused to obtain a laminate having three layers.

Example 9 A foamed polyurethane sheet having a thickness of 10 mm was adhered to the laminate obtained in Example 4 via a vinyl acetate resin emulsion-based adhesive, and an aluminum foil having a thickness of 10 μm was further adhered. As a result, a laminate including four layers shown in FIG. 5 was obtained.

Example 10 1 kg of wall mortar was dissolved in 1 liter of water, and 25 cm × 25 cm × 5 c made of an acrylic plate (5 mm thick)
m. In a state where the mortar is semi-dried, the zeolite-supporting paper prepared in Production Example 1 is placed thereon,
It was left until completely hardened. The mold was removed, and a surface opposite to the surface to which the zeolite-carrying paper was adhered was coated with colloidal silica in which titanium dioxide was dispersed to a thickness of 50 μm to obtain a laminate.

The laminate obtained in Example 1 has an excellent surface texture and tactile sensation, and can be used to remove bad odors. The laminate obtained in Example 2 is suitably used as a deodorant sheet for disposable diapers or sanitary products, and the laminate obtained in Example 3 is suitably used as a freshness preserving sheet for fruits and vegetables. The laminate obtained in Example 4 has high strength by sandwiching a polyethylene nonwoven fabric between supporting papers and has excellent gas permeability, so that it is suitably used as a filter for gas phase and liquid phase.
The laminates of Examples 7 and 8 are also suitably used as a gas phase and liquid phase filter as in Example 4. In particular, the laminate of Example 8 is useful as a gas-phase filter because it has a high ability to adsorb nonpolar molecules as well as polar molecules. The laminate obtained in Example 5 is suitably used as a cation exchange sheet, and the laminate of Example 6 is further preferably used as an antibacterial sheet since copper ions have antibacterial properties. The laminate obtained in Example 9 is excellent in heat insulation, buffering properties and electromagnetic wave resistance, adsorbs odorous gas, and has high strength, so that it is suitably used as a panel for building materials. The laminate of Example 10 is also suitably used as a building material panel as in Example 9, and has a photocatalytic ability by titanium dioxide.

[0044]

The laminate of the present invention is obtained by laminating an inorganic porous crystal-hydrophilic polymer composite on a function-improving base material not containing an inorganic porous crystal, thereby obtaining an inorganic porous crystal-hydrophilic polymer composite. Gas adsorption ability, volatile organic solvent removal ability,
In addition to flame retardancy, heat retention, ability to remove heavy metals and radioactive elements, it has high strength, can further improve tactile sensation such as touch, and is useful as a material having further functionality.
Furthermore, by supporting a metal on the inorganic porous crystal,
It is possible to provide a laminate further provided with antibacterial properties, odor eliminating ability and the like.

[Brief description of the drawings]

FIG. 1 is a view showing a preferred embodiment of a laminate of the present invention in which an inorganic porous crystal-hydrophilic polymer composite is an inorganic porous crystal-supported pulp composite.

FIG. 2 is a view showing another preferred embodiment of the laminate of the present invention in which the inorganic porous crystal-hydrophilic polymer composite is an inorganic porous crystal-supported pulp composite.

FIG. 3 is a view showing a preferred embodiment of the laminate of the present invention when the layer composed of the inorganic porous crystal-hydrophilic polymer composite is in the form of a film.

FIG. 4 is a view showing a preferred embodiment of the laminate of the present invention when the layer made of the inorganic porous crystal-hydrophilic polymer composite has a cylindrical shape.

FIG. 5 is a view showing a preferred embodiment when the laminate of the present invention is in the form of a composite sheet.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Fibrous function improving base material 1 'Film-shaped function improving base material 2 Layer composed of inorganic porous crystal-hydrophilic polymer composite fiber 2' Inorganic porous crystal-hydrophilic polymer composite film Layer consisting of 2 "cylindrical inorganic porous crystal-hydrophilic polymer composite

Continuation of the front page (72) Inventor Yoshinobu Fujimoto 4-1-1, Okai, Fukushima-ku, Osaka City Rengo Co., Ltd. Central Research Laboratory

Claims (7)

[Claims] 1. A laminate characterized in that a hydrophilic polymer has a layer comprising an inorganic porous crystal-hydrophilic polymer composite having an inorganic porous crystal in its body and a function-enhancing substrate. 2. The function-improving base material is a plastic film,
Claims characterized by comprising at least one selected from the group consisting of regenerated cellulose films, metal foils, natural fibers, semi-synthetic fibers, synthetic fibers, metal fibers, inorganic fibers, activated carbon fibers, inorganic hardeners and inorganic films. Item 7. The laminate according to Item 1. 3. The hydrophilic polymer is composed of natural cellulose, regenerated cellulose, bacterial cellulose, chemically modified cellulose, silk, wool, polyacrylamide, polyvinyl alcohol, crosslinked polyvinyl alcohol, chitin, chitosan, ethylene vinyl acetate copolymer and polyvinyl formal. The laminate according to claim 1, comprising at least one member selected from the group consisting of: 4. The laminate according to claim 3, wherein the natural cellulose is at least one selected from the group consisting of pulp, cotton, hemp, and kenaf. 5. The laminate according to claim 3, wherein the chemically modified cellulose is at least one selected from the group consisting of ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl hydroxyethyl cellulose, and carboxymethyl cellulose. 6. The laminate according to claim 1, wherein the inorganic porous crystal is zeolite. 7. The laminate according to claim 1, wherein the inorganic porous crystal carries at least one metal selected from the group consisting of silver, copper, zinc, iron, nickel, cobalt, palladium and platinum. body.