JP2001001479A - Decorative material having moisture absorbing/releasing performance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent stain resistance without lowering moisture absorbing/releasing performance by forming a surface protective layer made of a moisture permeable urethane resin on a surface of the resin. SOLUTION: A moisture absorbing/releasing resin layer 1 and a surface protective layer 3 made of a moisture absorbing/releasing urethane resin formed on a surface of the layer 1 are formed. The layer 1 is made of a resin composition containing a moisture absorbing/releasing material 2. As the material 2 to be added into the layer 1, an activated clay having good film manufacturing and coating suitability is most preferred. The material 2 is in a fine particle-like state and is uniformly dispersed in the resin, and its adding amount into the resin of 50 to 150 pts. to 100 pts. of the resin content is preferred. In the case of using the decorative material as wall paper or the like, as a base material 4, paper, or fiber is used, and a moistureproofing and waterproofing layer 5 is preferred to be formed on a front surface, a rear surface or both the surfaces of the material 4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative material having moisture absorbing and releasing performance, which is used as an interior material for buildings such as houses.

[0002]

2. Description of the Related Art Conventionally, as a decorative material for interior decoration such as wallpaper,
A structure in which a polyvinyl chloride resin layer is formed on a base material such as paper is used. However, the cosmetic material having this configuration has poor moisture absorption and desorption properties, and is liable to cause dew condensation, mold, ticks, and the like on the surface of the cosmetic material, and fluctuations in the humidity in the dwelling may adversely affect human health. In addition, since a polyvinyl chloride resin is used, chlorine-based gas is generated at the time of disposal or incineration, and there is an environmental problem.

[0003] In order to solve such a problem, a moisture-absorbing and desorbing material comprising a non-vinyl chloride resin-based resin composition such as an ethylene-vinyl acetate copolymer containing a moisture-absorbing and desorbing material such as activated clay on a substrate is proposed. A decorative material on which a resin layer is formed has been experimentally manufactured (for example, Japanese Patent Application Laid-Open No. 11-5862).

[0004] This cosmetic material has excellent moisture absorption / desorption performance, and is less likely to cause environmental pollution since it uses a non-vinyl chloride resin. However, in the case of the decorative material having such a configuration, since the formed moisture-absorbing / desorbing resin layer has high moisture permeability, dirt (especially water-soluble dirt) easily penetrates into the interior,
There is a problem that dirt is difficult to wipe off.

[0005]

Therefore, in order to improve the stain resistance, there has been developed a decorative material having a moisture-absorbing and desorbing resin layer provided with a stain-resistant surface protective layer made of a two-component curable urethane resin on the surface thereof. it was thought. However, although this has excellent contamination resistance performance, since a coating film is formed on a resin layer having moisture absorption / release performance, water vapor to the moisture absorption / release material present in the moisture absorption / release resin layer is present. , And sufficient moisture absorption / release performance could not be obtained.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a cosmetic material which is provided with excellent stain resistance without lowering the moisture absorption / release performance. It is in.

[0007]

According to the present invention, in order to solve the above-mentioned problems, a surface protection layer made of a urethane resin having moisture permeability (moisture-permeable urethane resin) is formed on the surface of a moisture-absorbing and releasing resin layer. Provided is a cosmetic material having moisture absorbing and releasing performance.

The decorative material of the present invention preferably has a moisture absorbing / releasing resin layer and a surface protective layer made of a moisture permeable urethane resin laminated on a substrate surface in this order. A moisture-proof / waterproof layer is further laminated on the back surface of the resin layer, the front surface of the base material, or the back surface of the base material.

The cosmetic material of the present invention has excellent anti-smudge performance while maintaining excellent moisture-absorbing and desorbing properties, and is less likely to adhere to dirt such as food, drink, ink, and crayon, and is easy to remove dirt.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the decorative material of the present invention will be described in detail. The cosmetic material of the present invention basically has the configuration shown in FIG.
As shown in (a), the moisture absorbing / releasing resin layer 1 and the surface protective layer 3 made of moisture-permeable urethane resin on the surface of the moisture absorbing / releasing resin layer 1.
Is formed. Further, the moisture-absorbing and releasing resin layer 1 is made of a resin composition containing a moisture-absorbing and releasing material 2.

The hygroscopic material 2 added to the hygroscopic resin layer 1 includes inorganic materials such as activated clay, acid clay, sepiolite, diatomaceous earth, tobermorite, zeolite and silica gel, and a graft of starch and acrylonitrile. Any of organic materials such as a saponified copolymer and a crosslinked polyvinyl alcohol can be used.

Of these, inorganic ones are preferably used because of the reproducibility of repeated cycles of moisture absorption and desorption, the absence of swelling due to moisture absorption, and the fact that they have fungicidal properties. Among them, activated clay having good compatibility with the resin 1 and good film forming and coating suitability of the resin composition added to the resin 1 is more preferable.

Activated clay (also referred to as "montmorillonite") is clay that has been acid-treated to increase its activity. Normally, natural acid clay or clay similar thereto is dried at room temperature to form a powder, which is heated at a temperature of 90 ° C. or more under normal pressure or pressure with an appropriate amount of an acid such as sulfuric acid. After that, what was separated by filtration, washed and dried at 120 to 200 ° C. is used. Activated clay is known to have high moisture absorption / desorption performance due to its strong adsorption characteristics and the distribution of porous pore sizes.

Activated clay is a powerful moisture absorbing and releasing agent and does not dissolve in or swell with water. In addition, even if exposed for a long time in the air, it is possible to repeat moisture absorption and release without deteriorating or producing mold.

The moisture-absorbing / desorbing material 2 is preferably used in the form of fine particles (moisture-absorbing / desorbing fine particles) which are uniformly dispersed in the resin without causing separation and sedimentation. By containing the fine particles in the resin, as described later, a part of the fine particles is extruded from the inside of the resin layer to the resin surface when the film is formed, thereby increasing the surface density of the particles exposed on the resin surface. Can be. Further, the moisture absorption / release resin layer 2 is made porous by the shear stress between the particles and the surrounding resin, and the particles inside the resin layer also circulate with the outside air. be able to.

The average particle size of the hygroscopic material 2 is as follows:
It is preferably about 0.1 to 100 μm. Further, the average pore diameter is preferably 10 to 60 ° in order to keep the humidity at 40 to 60%, and particularly preferably about 20 to 30 ° in terms of the moisture absorption / release effect.

The amount of the hygroscopic material 2 added to the resin is 50 to 50 parts by weight based on 100 parts by weight of the resin (binder).
About 150 parts by weight is preferable. When the amount is less than 50 parts by weight, the moisture absorption / release performance is not sufficiently exhibited. On the other hand, when it is added in an amount of 150 parts by weight or more, the composition obtained by adding the moisture-absorbing / desorbing material to the water-dispersed emulsion increases the viscosity, and the coating suitability decreases.
Further, the strength of the moisture-absorbing / releasing resin layer obtained as a coating film is reduced and the resin layer becomes brittle.

When an acidic substance such as activated clay is used as the moisture absorbing / releasing material 2, it is more preferable that the resin 1 contains an alkaline additive in addition to the moisture absorbing / releasing material 2. Acid hygroscopic materials such as activated clay can cause yellowing, etc. as a result of a light resistance test and a heat resistance test (a test for accelerating the effect of sunlight entering through a window) on a resin in which the acidity is dispersed. . In the present invention, in order to avoid such a problem, it is preferable to suppress the light yellowing resistance by adjusting the pH by mixing an alkaline additive together with the acidic moisture absorbing / releasing material in the resin.

Examples of such alkaline additives include ammonia (aqueous ammonia), hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, and hydrogen carbonate such as sodium hydrogen carbonate and potassium hydrogen carbonate. Salts and the like can be mentioned. The amount of the alkaline additive to be added is, for example, about 10% by weight or more, preferably about 20% by weight of activated clay in the case of aqueous ammonia (28% by weight).

The resin containing the moisture-absorbing / desorbing material 2 is not limited as long as it can hold the moisture-desorbing / desorbing material 2 and can be formed in a layered form. Etc. can be used. These resins are preferred because they are non-vinyl chloride resins, can disperse moisture-absorbing and desorbing materials uniformly, and are excellent in film forming (or coating) suitability and processing characteristics.

As the polyolefin resin, for example,
Ethylene-based unsaturated monomers such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl alcohol copolymer and other polymerizable monomers And terpolymers such as polyethylene, polypropylene, polybutene, and homopolymers consisting solely of ethylenically unsaturated monomers such as polymethylpentene, for example, ethylene-propylene copolymers and ethylene- Copolymers of ethylenically unsaturated monomers such as propylene-butene copolymer can be exemplified.

The acrylic resin is mainly made of acrylic acid (including methacrylic acid) and its derivatives such as acrylamide and acrylonitrile, which are obtained by polymerizing acrylic resin, other acrylates, ethylene, styrene and the like. Is a copolymer resin with a monomer.

Examples of such an acrylic resin include poly (methyl meth) acrylate, poly (meth) ethyl acrylate, poly (butyl) methacrylate, and methyl (meth) acrylate-butyl (meth) acrylate. Coalescing,
(Meth) acrylic acid such as methyl (meth) acrylate-2-hydroxyethyl (meth) acrylate, ethylene-methyl (meth) acrylate, and styrene-methyl (meth) acrylate Those composed of a homo- or copolymer containing an ester are exemplified. Here, (meth) acrylate is used in the meaning of acrylate and methacrylate. Of these,
Those having a glass transition temperature of 15 to 60 ° C are preferred.

Alternatively, a mixed resin of one or more of an acrylic resin and a polyolefin resin, for example, a mixed resin of an ethylene-vinyl acetate copolymer and an acrylic resin can be used.

Of these, the resin itself has a certain degree of moisture absorption / desorption properties, is well compatible with the moisture absorption / desorption material, and has good dispersibility of the moisture absorption / desorption material, so that the amount of addition can be increased. For some reasons, it is particularly preferable to use an ethylene-vinyl acetate copolymer or a saponified product thereof.

In forming the moisture-absorbing / desorbing resin layer 1, the above-mentioned resin may contain, in addition to the moisture-absorbing / desorbing material 2 and, if desired, an alkaline additive, and if necessary, other additives. . Other additives include, for example, flame retardants such as magnesium hydroxide and aluminum hydroxide, fungicides such as 10,10'-oxybisphenoxyarsine, antibacterial agents such as zeolite carrying silver ions, and organic amino compounds. Formaldehyde scavengers, extenders such as calcium carbonate, calcium silicate, barium sulfate, etc., hindered amine radical scavengers such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, piperidine radical scavengers, etc. Light stabilizers such as radical scavengers, antioxidants such as alkylphenols, amines and quinones, various ultraviolet absorbers such as benzophenone, salicylate, benzotriazole and acrylonitrile, silicon-based or non-silicone-based Foaming agents, dispersants such as polycarboxylic acids, titanium white, carbon black Color pigments such as phthalocyanine blue, heat stabilizers,
In addition to the plasticizer, a foaming agent and the like can be mentioned.

When a foaming agent is added, a resin having a large number of cavities in the resin layer, for example, as shown in FIG. The wet resin layer 1 can be formed. In such a case, the air permeability is good, and a product excellent in moisture absorption / release properties can be obtained.

As the foaming agent to be used, for example, those listed in the following (1) to (3) can be used.

(1) polyvinyl chloride resin, polyvinylidene chloride resin, acrylonitrile-vinyl chloride copolymer,
A microcapsule-type foaming agent containing a volatile, heat-expandable substance such as butane, hexane, and pentane in a hollow body of a resin such as a vinylidene chloride-acrylonitrile copolymer,
(2) azodicarbonamide, azobisisobutyronitrile, 4,4′-oxybisbenzenesulfonylhydrazide, N, N-dinitrosopentamethylenetetramine,
Pyrolytic foaming agents such as sodium bicarbonate, ammonium carbonate, sodium borohydride, and, if necessary, metal soaps such as lead, zinc, calcium, and tin, dibasic lead sulfate, tribasic (3) A mixture of (1) and (2) above, to which a foaming accelerator such as lead or zinc white is added.

The amount of the foaming agent to be added is usually preferably about 1 to 10 parts by weight based on 100 parts by weight of the resin. If the addition is less than 1 part by weight, the effect of adding a foaming agent is poor.
If the amount exceeds 0 parts by weight, the voids in the resin layer become too large and the surface irregularities become large, which is not preferable.

The film-forming or coating of the resin composition containing the moisture absorbing / releasing material 2 can be carried out in the form of an organic solvent solution, a heated melt or the like. It is preferably used in the form of an emulsion. That is, if desired, an alkaline additive is added to an aqueous dispersion emulsion of a mixed resin comprising one or more of a polyolefin resin and an acrylic resin, and the pH of the emulsion is adjusted.
Is preferably in the alkaline region.

Acidic moisture-absorbing and desorbing materials such as activated clay exhibit strong acidity due to the residue of the sulfuric acid treatment performed to increase the activity and basic components eluted by the acid treatment. For this reason, it is difficult to completely neutralize the emulsion, so it is preferable to make the emulsion apparently in an alkaline region. In consideration of worker's safety, the pH value should be 8-11.
It is preferable to set to about.

In the decorative material of the present invention, a surface protective layer 3 made of a moisture-permeable urethane resin is formed on the surface of the moisture-absorbing and releasing resin layer 1. The moisture-permeable urethane resin is a one-pack type polyurethane resin in which a group having affinity for water (referred to as a hydrophilic group) is introduced into a polyurethane structure.

The one-pack type polyurethane resin is obtained by reacting an excess of diisocyanate with a polyhydric alcohol (polyol) to leave a free isocyanate group, and the isocyanate group reacts and cures with moisture (so-called one-pack moisture-curable polyurethane resin). ), An isocyanate group that is strongly active even at ordinary temperature is protected with a compound such as a suitable phenol to make it inactive, and the isocyanate group is regenerated by heating, and the isocyanate group reacts with the hydroxyl group of the polyol and cures (so-called). Thermosetting one-component polyurethane resin).

The coating film of such a moisture-permeable urethane resin is formed as a nonporous layer having no pores, and has the property of allowing moisture to penetrate into the layer through hydrophilic groups. Examples of such a hydrophilic group include an unreacted hydroxyl group, carboxyl group, amino group, and sulfonic acid group.

As a method of introducing such a hydrophilic group into the polyurethane structure, for example, one or both of a polyol and an isocyanate which are constituent components of the polyurethane may be added to (meth) acrylic acid, maleic acid, fumaric acid, itacone A method of copolymerizing a monomer such as an unsaturated carboxylic acid having a carboxyl group such as an acid, a vinyl compound having an amino group such as acrylamide, a vinyl sulfonic acid having a sulfonic acid group such as ethylene sulfonic acid, or a polyol and an isocyanate One or both of
There is a method such as a method in which a vinyl acetate monomer is copolymerized and then saponified to introduce a hydroxyl group.

In a coating film made of a moisture-permeable urethane resin, as the number of hydrophilic groups introduced into the molecule increases, the moisture permeability increases, but on the other hand, swelling of the coating film causes problems in terms of design. Therefore, from the viewpoint of the design of the coating film to be formed, it is preferable to adjust the swellability so that the area expansion of the coating film due to water is within a maximum of 15%. The swellability of the moisture absorbing / releasing resin layer can be adjusted by the amount of the hydrophilic group introduced. The moisture-permeable urethane resin has a moisture permeability of 1 when the coating film is formed.
5000 g / m ² · 24 hrs. It is preferable to use the above. The conditions for measuring the moisture permeability are as follows:
Based on IS-Z-0208, temperature 40 ° C, humidity 90%
The measurement time at RH is 24 hours.

The method for forming the surface protective layer 3 by applying the moisture-permeable urethane resin on the moisture-absorbing / releasing resin layer 1 is as follows.
Gravure coating, comma coating, spray coating and the like.

Hygroscopic resin layer 1 including the surface protective layer 3
Has a thickness of usually 1 to 300 μm, preferably about 1 to 10 μm. If the thickness of these layers is too small, the stain resistance becomes insufficient, and if the thickness is too large, the moisture absorption / release performance becomes insufficient.

Further, as shown in FIG. 1B, the decorative material of the present invention has a structure in which a moisture absorbing / releasing resin layer 1 and a surface protective layer 3 are sequentially laminated on a base material 4. Is also good.

The substrate 4 serves as a support for producing a moisture absorbing / releasing decorative material. The shape of the substrate may be sheet-like or plate-like. Cedar, cypress, zelkova,
Wood veneers such as oak, lauan, teak, and melapie, wood veneers such as wood veneer, wood plywood, particle board, and wood fiber board such as medium density fiber board (MDF), iron, iron alloy,
Copper, copper alloy, metal such as aluminum, acrylic resin, polycarbonate resin, ethylene-vinyl acetate copolymer,
Resins such as ethylene vinyl acetate, polyester resin, polystyrene, polyolefin resin, ABS resin, phenol resin, polyvinyl chloride, cellulosic resin, rubber, various glasses, ceramics such as ceramics, cement such as ALC (foamed lightweight concrete), and silicic acid calcium,
Non-cement ceramic materials such as gypsum; paper such as high-quality paper, Japanese paper, and base paper for wallpaper; and nonwoven fabrics or woven fabrics made of fibers such as carbon, asbestos, potassium titanate, glass, and synthetic resins. Further, the base material may be colored with a coloring agent.

When the decorative material is used as a sheet (decorative sheet) such as a wallpaper, the basis weight of the base material 4 is 20 to 120.
It is preferable to use paper such as high-quality paper, thin paper, backing paper for wallpaper, Japanese paper, etc. of about g / m ² , or woven or non-woven fabric made of fibers such as glass fiber, asbestos, polyester fiber, and vinylon fiber. In the case of paper, a flame retardant such as aluminum hydroxide powder may be added.

When a material having moisture absorption / desorption properties or water permeability such as paper or wood is used as the base material 4, the moisture adsorbed by the moisture absorption / desorption resin layer 2 passes through the base material and its back surface (for example,
(The interior of the wall). In some cases, the back surface may be moistened, warped, or cause mold or rust due to moisture permeating the back surface.

To prevent this phenomenon, for example, as shown in FIG. 1D, the surface of the base material 4 (on the side of the moisture-absorbing / desorbing resin layer), the back surface of the base material 4 or the front and back surfaces of the base material 4 It is preferable to form a moisture-proof / waterproof layer 5 of polyethylene, polyvinylidene chloride, silica-deposited polyethylene terephthalate, aluminum-deposited polyethylene terephthalate, or the like. When the moisture-proof / waterproof layer 5 has a layer structure without a base material as shown in FIG. 1A, a moisture-proof / waterproof layer is provided on the back surface (the side opposite to the surface protective layer) of the moisture-absorbing and releasing resin layer. Form.

The thickness of the moisture-proof / waterproof layer 5 is usually 30 to 10
A thickness of about 0 μm is sufficient, and is bonded to the front surface, the back surface or both the front and back surfaces of the base material 4 or the back surface of the moisture absorbing / releasing resin layer with an adhesive such as a two-component curable urethane resin, or a melt extrusion method (extrusion). It can be formed by coating with a coating method) or the like.

Further, in the cosmetic material of the present invention, for the purpose of improving the decorativeness, as long as the moisture absorption / release properties are not impaired,
A decorative layer can also be formed on the surface of the moisture-absorbing and releasing resin layer (if the resin layer is transparent, it can be on the back surface of the resin layer or the surface of the substrate).

As a method for forming the decorative layer, for example, the base material or the moisture absorbing / releasing resin layer itself is colored by adding a pigment, or a pattern is provided on the substrate or the moisture absorbing / releasing resin layer by pattern printing or the like. There is a way. When a picture layer is formed on the moisture-absorbing and releasing resin layer, it is necessary to partially form a decorative layer in order to exhibit the function of the moisture-absorbing and releasing material.

As the pattern printing, a pattern can be formed with ink (or paint) by using a known printing method such as gravure printing, offset printing, silk screen printing, and transfer printing from a transfer sheet.

Examples of the pattern include a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather pattern, a geometric pattern, a character symbol, and a solid surface.

As the ink or paint, a binder,
Pigments, coloring agents such as dyes, and, if necessary, extender pigments,
A mixture in which a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like are appropriately mixed can be used. As the binder, for example, vinyl chloride-vinyl acetate copolymer, acrylic resin,
Urethane resin, chlorinated polyolefin, or a mixture thereof can be used.

Examples of the coloring agent include inorganic pigments such as titanium white, carbon black, nickel titanium yellow, red iron oxide, ultramarine, quinacridone red, isoindolinone, and the like.
Organic pigments such as phthalocyanine blue, and pearl pigments composed of titanium dioxide-coated mica foil powder.

Further, the surface can be embossed with a concavo-convex pattern, or the embossed concave portions can be filled with a coloring ink by wiping to be colored.

The decorative material of the present invention can be manufactured, for example, as follows. (1) Method of coating and forming hygroscopic resin layer 1 and surface protection layer 3 on base material 4 or support sheet 6 (see FIG. 2) First, a resin made of acrylic resin or polyolefin resin is used. In addition, a moisture-absorbing / desorbing material 2 and, if desired, additives such as an alkaline additive and a dispersant are blended in a predetermined ratio to prepare a resin composition, and the resin composition is placed on the base material 4 or the support sheet 6. After coating and solidifying by drying and heating to form the moisture-absorbing / releasing resin layer 1, it can be manufactured by laminating the surface protective layer 3 having stain resistance on the moisture-absorbing / releasing resin layer 1. it can.

In order to form the moisture absorbing / releasing resin layer 1, more specifically, the liquid composition (water-dispersed emulsion or the like) is coated on a substrate by using a coating machine such as a roll coater, a comma coater, or a curtain floater. ) With a thickness of 50 to 300 μm, for example, at 120 to 200 ° C. for 30 seconds to 1
Drying by heating for a period of time, and then,
By solidifying by heating and drying for about 30 seconds to 1 hour.

When a foaming agent is added to the resin composition, it can be foamed to obtain a laminate of the base material and the moisture-absorbing and releasing resin layer. In the case where the moisture-absorbing and releasing resin layer 1 is a cellular foam as shown in FIG. 1 (c), if a moisture-permeable urethane resin is applied after foaming, the surface becomes uneven and the coating is not uniform. Because it is not possible to exhibit sufficient stain resistance, apply in an unfoamed state,
Thereafter, it is preferable to perform foaming.

(2) A moisture absorbing and releasing resin sheet (which corresponds to the moisture absorbing and releasing resin layer 2) and a moisture-permeable film having stain resistance (which corresponds to the surface protective layer 3) are laminated (laminated). )how to

In this case, as shown in FIG. 2 (a), the support sheet 6 is used as a base material, and, for example, in the same manner as in the case of the above-mentioned laminated body, for example, a resin made of the acrylic resin or polyolefin resin or the like. A water-dispersible material 2 and, if desired, a liquid composition prepared by mixing an alkaline additive in a water-dispersed emulsion, on a support sheet 6 having releasability, and solidifying by heating and drying to form a moisture-absorbing and releasing resin layer. 1
Is formed, and a separately prepared moisture-permeable film 3 having stain resistance is adhered to the moisture-absorbing / desorbing resin layer 1 by, for example, a heat laminating method. Then, as shown in FIG. By peeling the support sheet 6 from the moisture-absorbing and releasing resin layer 1, a moisture-absorbing and releasing cosmetic material as shown in FIG. 2 (c) can be obtained.

The support sheet 6 is not particularly limited as long as it has releasability from the moisture-absorbing and releasing resin sheet. For example, among the substrates listed above, a substrate having releasability can be used.

The decorative material of the present invention can be used by being laminated on another adherend. In the case of lamination, the adhesive layer can be omitted when the decorative material itself can be bonded to the adherend (by heat fusion or the like). If the decorative material itself does not adhere to the adherend, it is laminated with an appropriate adhesive. The adherend is the final product, and there may be cases where an interior decoration material is laminated for the surface decoration, or if necessary, for the purpose of reinforcing the mechanical strength of the interior decoration material, or for imparting concealment, The adherend may be laminated on the back surface of the decorative material.

There are various materials for the adherend. Examples of the shape include a plate material such as a flat plate and a curved plate, a three-dimensional article, a sheet (or film), and the like. Materials used for any of these shapes include wood veneers made of various tree species such as cedar, oak, lauan, and teak, wood materials such as wood plywood, particle board, medium density fiberboard (MDF), iron, aluminum, and the like. Metal, acrylic resin, polycarbonate resin, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, polyester resin, polystyrene, olefin resin, ABS resin, phenol resin,
Resins such as polyvinyl chloride, cellulosic resin, rubber, etc., materials exclusively used as plate materials or three-dimensional articles include glass, ceramics such as ceramics, cement such as ALC (foamed lightweight concrete), calcium silicate, gypsum, etc. Non-cement ceramic materials, materials used exclusively as sheets (or films) include high-quality paper, paper such as Japanese paper, or carbon, asbestos, potassium titanate, glass,
There is a nonwoven fabric or a woven fabric made of a fiber such as a synthetic resin.

The cosmetic material of the present invention is installed in a place where dirt is likely to adhere. For example, walls, floors, building interiors such as ceilings, doors, handrails, door frames, window frames and other fittings or features,
It can be suitably used as a cosmetic material for surfaces of various members requiring a moisture absorbing and releasing function, such as furniture such as cabinets, vehicle interiors such as automobiles and trains, interiors of aircrafts and ships, partitions, containers and the like.

[0062]

The present invention will be described in more detail with reference to the following examples. The following examples are merely examples of the embodiments of the present invention, and without departing from the spirit of the present invention, the types of the moisture-absorbing and desorbing materials, the types of the resin of the moisture-absorbing and desorbing resin layer, the types of the base material, The layer configuration, the thickness of each layer, the presence or absence of a picture layer, and the like can be freely designed and changed.

Example 1 An aqueous emulsion having the following composition [A] was prepared by mixing 23 parts by weight of activated clay (Galeon Earth V2R, manufactured by Mizusawa Chemical Co., Ltd.) 2a having an average particle diameter of 20 μm and an average pore diameter of 25 °. 28.5 parts by weight to prepare a dispersion, which was coated on a substrate 4a of a backing paper having a basis weight of 150 g / m ² (manufactured by Tokushu Paper) with a thickness of 170 μm. And heated at 120 ° C. for 1 minute to solidify the aqueous resin emulsion layer (coated layer) and absorb and release the moisture-absorbing / desorbing resin layer 1a.
Was formed. Thereafter, an aqueous urethane resin (trade name: Daiplacoat AQW surface treatment agent, manufactured by Dainichi Seika Kogyo Co., Ltd.) is applied on the moisture absorbing / releasing resin layer 1a by a gravure coating method at a thickness of 3 μm (at the time of drying). C. for 1 minute to solidify the aqueous urethane resin to form a surface protective layer 3a. Further, the foaming was completed by heating at 170 ° C. for about 1 minute to obtain a decorative sheet of Example 1 as shown in FIG.

[A] Resin binder: ethylene-vinyl acetate copolymer: 23 parts by weight (manufactured by Chuo Rikagaku Kogyo Co., Ltd., product number: BE-920) Blowing agent: microcapsule type blowing agent: 3.5 parts by weight (Matsumoto Yushi Co., Ltd., product number: F-85) Dispersant: 1 part by weight of polycarboxylic acid Defoaming agent: 1 part by weight of non-silicon-based defoaming agent 28.5 parts by weight in total

Comparative Example 1 23 parts by weight of activated clay (Galeon Earth V2R, manufactured by Mizusawa Chemical Co., Ltd.) having an average particle diameter of 20 μm and an average pore diameter of 25 ° were dispersed in an aqueous emulsion of the above composition [A]. To prepare a dispersion, which was weighed 150 g /
m ² backing paper (made by Tokushu Paper Co., Ltd.)
Coated with a thickness of 170 μm. Then at 120 ° C for 1
The aqueous resin emulsion layer (coated layer) was solidified by heating for minutes. Thereafter, by heating at 170 ° C. for about 2 minutes, foaming of the aqueous resin emulsion layer was completed to form the moisture-absorbing and releasing resin layer 1b, and the decorative sheet of Comparative Example 1 as shown in FIG. Obtained.

[0066] Using an aqueous emulsion of the same composition as the (A) except that no addition of Comparative Example 2 activated clay, others in the same manner as in Comparative Example 1, to obtain a decorative sheet of Comparative Example 2.

[0067] using a decorative sheet produced by the humidity modulating effect Test Example 1 and Comparative Examples 1 and 2 were subjected to humidity control effect test by the following method.
That is, the decorative sheets of Examples and Comparative Examples 1 and 2 were cut into a size of 25 cm × 25 cm on the inner wall surface of an aluminum case having an inner size of 25 cm × 25 cm × 25 cm, and each sheet was bonded to the inner wall surface of the aluminum case. After the initial setting temperature is constant at 20 ° C. and 50% RH, the aluminum case is sealed, and the ambient temperature is 20 ° C. for 0.5 hour.
The temperature was changed in a cycle of 2 hours at 30 ° C., 2 hours at 20 ° C., and 2 hours at 10 ° C., and the humidity change in the aluminum case was measured. FIG. 4 shows the results. In the figure, Example 1 is shown.
Shows the results for the case of the decorative material of Comparative Example 1 and the results for the case of the decorative material of Comparative Example 2.

From the measurement results, it was found that the decorative sheet of Example 1 was
The moisture absorption / release performance was equivalent to that of the decorative sheet of Comparative Example 1 without the surface protective layer. The decorative sheets of Example 1 and Comparative Example 1 are:
The fluctuation range of humidity was converged as compared with the decorative sheet of Comparative Example 2 in which no moisture absorbent was added, and it was found that these had excellent moisture absorbent performance.

Stain resistance evaluation test The contaminants shown in Table 1 below were dropped onto the surfaces of the decorative sheets prepared in Example 1 and Comparative Examples 1 and 2, and after 24 hours, JK wiper (Crecia Co., Ltd.) was used. Product number:
(150-S). The results are shown in Table 1 below. In Table 1, when no trace of dirt is found by wiping with water, ○, dirt is not removed by wiping with water, but after gently wiping with a synthetic detergent stock solution, wiping with water and then wiping with dry cloth When the mark disappeared, the evaluation result was indicated by Δ, and when any trace of stain remained, the evaluation result was indicated by X.

[0070]

[Table 1]

As a result, it was found that the decorative sheet of Example 1 had excellent stain resistance as compared with the decorative sheets of Comparative Examples 1 and 2.

[0072]

As described above, the decorative material of the present invention is a decorative material having excellent moisture absorption / desorption performance and excellent contamination resistance. That is, by providing a surface protective layer made of urethane resin having moisture permeability on the surface of the moisture-absorbing / desorbing resin layer, it is resistant to stains caused by coffee, food and drink such as soy sauce, water-based ink, crayon, and easily removes these stains. Can be removed.

When the decorative material of the present invention further has a moisture-proof / water-proof layer between the moisture-absorbing and releasing resin layer and the base material or on the back surface of the base material, moisture permeates into the back surface of the base material, The rear surface does not become moist, warp, or cause inconvenience such as mold or rust.

[Brief description of the drawings]

FIG. 1 is a structural sectional view of a decorative material according to the present invention.
(A) is a moisture absorbing / releasing resin layer (or moisture absorbing / releasing resin sheet)
1 is a structural sectional view of a decorative material having a structure in which a surface protective layer (or a moisture-permeable and stain-resistant film) 3 is laminated on 1;
(B) is a structural cross-sectional view of a decorative material having a structure in which the moisture-absorbing and releasing resin layer 1 and the surface protective layer 3 are laminated on a base material 4;
(C) is a structural cross-sectional view of a decorative material having a structure in which a moisture-absorbing / desorbing resin layer 1 made of a cellular foam and a surface protective layer 3 are laminated on a base material 4. (D) is further moisture-proof on the back surface of the substrate 4.
FIG. 2 is a structural sectional view of a decorative material on which a waterproof layer 5 is formed.

FIG. 2 is a cross-sectional view showing main production steps of a decorative material of the present invention using a peelable support sheet as a base material.

FIG. 3 is a structural cross-sectional view of a decorative sheet prepared in Examples and Comparative Examples.

FIG. 4 is a diagram showing measurement results of a humidity control effect test.

[Description of Symbols] 1, 1a, 1b: moisture-absorbing and releasing resin layer (moisture absorbing and releasing resin sheet), 2, 2a, 2b ... moisture absorbing and releasing material, 3, 3a ... surface protective layer (moisture-permeable and stain-resistant film) ), 4,4a, 4
b: base material, 5: moisture-proof / waterproof layer, 6: support sheet, a ...
Cellular foam

Continued on front page F-term (reference) 2E001 DB03 FA10 GA12 GA24 GA25 GA42 HB02 HB04 HB05 HC01 HC02 HC04 HC11 HD07 HD11 HE01 JA01 JA02 JA04 JA06 JA07 JA24 JB03 JB04 JD04 LA04 4F100 AC10H AK01A AK41B AK68 BA10 BA05 BA02 BA10 BA02 BA02 BA13 CA01 CA23 DE04H DG10 DJ01 GB08 HB00 JD04B JD04D JD05D JD15A JD16A JL04 JL06

Claims (3)

[Claims] 1. A cosmetic material having moisture absorption / desorption performance, comprising a surface protection layer made of a moisture permeable urethane resin formed on the surface of a moisture absorption / desorption resin layer. 2. A decorative material having moisture absorbing and releasing properties, wherein a moisture absorbing and releasing resin layer and a surface protective layer made of a moisture permeable urethane resin are laminated on a substrate surface in this order. 3. A moisture-absorbing and / or moisture-absorbing makeup according to claim 1, wherein a moisture-proof / water-proof layer is further laminated on the back surface of the moisture-absorbing and releasing resin layer, the surface of the base material or the back surface of the base material. Wood.