JP2000296573A - Thermal insulation decorative sheet and thermal insulation member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate an insufficient heat insulation effect if cooling or heating is executed in summer or winter and a dew formation in a room with excellent heat insulation effect if heating is executed in winter by incorporating a heat insulation layer made of a cell-like resin and a decorative layer provided on the insulation layer. SOLUTION: A base material sheet for constituting a decorative layer 2 colored with a pigment c is prepared, and its one side or both side surfaces are corona discharged. The sheet is coated with a solution obtained by dissolving a resin composition blended with a foaming agent in a suitable organic solvent in a resin b used as a heat insulation layer by using a coating machine such as a roll coater, a comma coater or the like, dried, and solidified as a coating film. The coating film is heated and foamed to form the insulation layer 1 made of a cell-like resin, thereby obtaining a decorative sheet 10A. Thus, stability to temperature changes of indoor and outdoor, and excellent heat insulation effect can be obtained. Further, an energy conservation effect is obtained. If the outdoor temperature is lowered, no dew is formed, and excellent moistureproofing effect can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat insulating decorative sheet used for interior or exterior of buildings, fittings, vehicles, and the like (both are collectively referred to as "inside and exterior"). The present invention relates to a heat insulating member having the decorative heat insulating sheet provided on a substrate.

[0002]

2. Description of the Related Art Conventionally, in interior / exterior members using a metal substrate such as a wall plate obtained by laminating a decorative layer on a resin sheet to a decorative layer on a metal such as iron or aluminum, or the surface of another substrate. It has been practiced to make the surface thereof a pattern and a color tone such as natural wood.

[0003]

However, the interior and exterior members using a metal base material such as iron or aluminum generally have a high thermal conductivity. For example, when cooling or heating in summer or winter, the heat retaining effect is insufficient. And dew condensation occurs when the room is heated in the winter, for example.

[0004] In order to solve the above-mentioned problems, the present invention provides an insulating decorative sheet which has an excellent heat-retaining effect against external temperature changes and does not cause condensation inside, and a decorative sheet based on the decorative sheet. An object is to provide a heat insulating member provided on a material surface.

[0005]

In order to solve the above problems, the present invention provides a heat insulating decorative sheet comprising a heat insulating layer made of a cellular resin and a decorative layer provided on the heat insulating layer. provide.

In the heat insulating decorative sheet of the present invention,
The expansion ratio of the heat insulating layer is preferably 10 times or more.

In the heat insulating decorative sheet of the present invention,
When the decorative layer has a breaking elongation of 10 according to JIS-K7127 on a colored acrylic resin sheet subjected to a decorative treatment.
It is preferable that a transparent acrylic resin sheet of 0% or more is laminated.

In the heat insulating decorative sheet of the present invention,
It is preferable that a moisture-proof layer is further provided on the back surface, the front surface, or both the front and back surfaces of the heat insulating layer.

The present invention also provides a heat insulating member having a base material provided directly or via another layer on the back side of the heat insulating decorative sheet.

[0010] By adopting the heat insulating decorative sheet and the heat insulating member of the present invention as described above, it is possible to minimize the secondary influence due to a heat change applied from the outside of a base material such as a metal. Therefore, according to the present invention, it is possible to provide a heat insulating decorative sheet and a heat insulating member which have an excellent heat insulating effect (heat insulating effect), and which can particularly effectively prevent dew condensation due to heating or the like in winter. it can.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a heat insulating decorative sheet and a heat insulating member of the present invention will be described in detail. The decorative heat insulating sheet of the present invention is obtained by sequentially laminating a decorative layer on the front side and a heat insulating layer on the rear side.

1) Heat-insulating layer The heat-insulating layer is provided to prevent heat from being transmitted from the outside and prevent the base material from being heated or cooled by heat conduction. The heat insulating layer may be any material that can suppress heat conduction and heat transfer by convection from the decorative layer side to the base material side or vice versa. Thus, it can be formed from a heat insulating material provided with an air layer in which air is confined in a closed space.

As the heat insulating material used for the heat insulating layer, generally, for example, fibrous heat insulating materials such as hollow beads, cellular resin (details will be described later), rock wool, glass wool, insulation board and cellulose fiber ,
And other fibrous insulation materials such as animal and plant fibers, soft fiber materials, carbon fibers and potassium titanate, calcium silicate, basic magnesium carbonate, diatomaceous earth,
Powders such as diatomaceous earth insulating brick powder and refractory insulating bricks Castable refractory insulating materials, other granular and powdered thermal insulating materials such as cork and carbon powder, and granular and powdered insulating materials such as multilayer foil insulating materials and aluminum foil -Multilayer foil heat insulating materials and heat insulating structural materials such as slate are exemplified.

Of these, the present invention employs a cellular resin as the heat insulating layer. The cellular resin layer is shown in FIG.
As shown by (reference numeral 1 in the drawing), the structure has a large number of holes such as bubbles in the resin. As a typical production method,
A foaming agent such as a microcapsule foaming agent and / or a pyrolytic foaming agent is added to various resins, and foaming is performed by heating or a chemical reaction.

The use of the cellular resin layer for the heat insulating layer is as follows.
(A) By using a cellular resin for the heat insulating layer, it is possible to obtain a heat insulating decorative sheet and a heat insulating decorative member having a heat insulating layer having a low density and a high heat insulating resistance as compared with a heat insulating layer using hollow beads or the like. ,

(B) As the heat insulating layer is thicker, the higher the heat insulating effect, the higher the effect can be obtained. Therefore, by using the cellular resin for the heat insulating layer, a thick heat insulating layer can be easily formed. , To obtain excellent heat insulating effect, and,

(C) The heat-insulating layer made of the cellular resin has good flexibility of the heat-insulating layer as compared with the resin layer to which the hollow beads are added, and is suitable for bending processing such as V-cut processing and lapping processing of the sheet. Is also good.

The cellular resin constituting the heat insulating layer can be produced by various production methods. For example, the following methods and the like can be mentioned.

A method of adding a microcapsule type foaming agent and / or a pyrolytic type foaming agent to various resins.

The microcapsule type foaming agent used here is air, butane, pentane, or the like as a heat-expandable gas in a hollow microsphere shell of a hollow thermoplastic resin made of a resin such as polyacrylonitrile or polyvinylidene chloride. Those containing hexane and the like are included.

Examples of the thermal decomposition type foaming agent include organic compounds such as azodicarbonamide, azobisisobutyronitrile, oxybisbenzenesulfonylhydrazide, paratoluenesulfonylhydrazide, dinitrosopentamethylenetetramine, and hydrogencarbonate. Inorganic substances such as sodium, ammonium carbonate, sodium borohydride and the like can be mentioned. In the present invention, only one of the above listed blowing agents or a mixture of two or more thereof can be used.

The amount of the foaming agent varies depending on the type of the base resin, the type of the foaming agent, the foaming conditions, the presence or absence of the foaming promoting catalyst, and the like.
The amount is about 3 to 50 parts by weight with respect to parts by weight, and from this range, the amount of addition may be adjusted so as to obtain a desired expansion ratio as described below.

Alternatively, air, nitrogen,
A method in which a substrate such as carbon dioxide or butane is injected is extruded from a T-die, cooled and solidified, or by other methods. Among these, the production method is preferred from the viewpoint that a high expansion ratio can be easily obtained and the heat insulation effect of the cellular resin is good.

In order for the cellular resin to function effectively as a heat insulating layer, the thermal conductivity is preferably 0.1 W / m.
K or less, more preferably 0.05 W / mK or less.
For that purpose, for example, the thickness of the heat insulating layer is 100 to 200.
In the case of about 0 μm, the expansion ratio (= the thickness of the heat insulating layer after foaming / the thickness of the heat insulating layer before foaming) is preferably 10 times or more, more preferably 20 times or more. If the expansion ratio is less than 10 times, the heat insulating effect of the bubbles will be insufficient. If the expansion ratio exceeds 30, the bubbles become large, and in addition to the heat conduction due to the diffusion of the gas molecule motion, the heat conduction due to the convection of the gas inside the bubbles also occurs. . Therefore, the expansion ratio is preferably 10 to 30 times, more preferably 20 to 30 times. The density of the cellular resin is preferably about 0.03 to 0.05 g / cm ³ .

The resin constituting the heat insulating layer is not particularly limited as long as it can hold a heat insulating material made of the cellular resin and can be formed into a predetermined shape. For example, polyolefin resin, acrylic resin, urethane resin, polyester resin, polystyrene, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polyamide resin, epoxy resin, phenol resin, and fluorine resin can be used. In addition, these resins may be crosslinked in order to harden the heat insulating layer and to give a hard tactile sensation.
Crosslinking is performed by a known method such as irradiation with ultraviolet light or an electron beam and addition of an organic peroxide. The crosslinking may be performed before or after the foaming of the heat insulating layer. However, when bending a heat insulating decorative sheet by lapping or the like, the crosslink density is suppressed to such an extent that bending suitability is not impaired.

In the present invention, among these, the use of a polyolefin resin is more preferable in terms of moldability and bending workability, and in particular, the ability to prevent dew condensation inside a heat insulating decorative member.

Examples of the polyolefin resin include polyethylene (low density, medium density or high density),
Polypropylene, polymethylpentene, homoolefin polymers such as polybutene, ethylene-propylene copolymer, propylene-butene copolymer, copolymers of different types of olefins such as ethylene-propylene-butene copolymer, ethylene- Vinyl acetate copolymer, ethylene-
Binary or ternary copolymers of olefins such as acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-vinyl alcohol copolymers and other polymerizable monomers, olefin-based thermoplastic elastomers And the like.

In order to form the heat insulating layer, as described later, a foaming agent is added to a heated melt of a binder resin containing a predetermined amount of the foaming agent, an organic solvent solution, or a resin emulsion (water dispersion suspension). Can be used in a predetermined ratio.

Next, a binder resin composition containing a predetermined amount of the above-listed blowing agents is applied or formed into a film, and (heated) foamed to form a resin layer having a large number of cellular bubbles in the resin layer. Can be formed. The bubbles in the heat insulating layer may be either closed cells or open cells, but are preferably closed cells from the viewpoint of heat insulation. In addition, the shape of each bubble can be various types such as a sphere, an ellipsoid, a regular polyhedron, and the size of each bubble can be almost the same, or the diameter of each bubble can be large. And a mixture with a small diameter. The diameter of the bubble is preferably about 10 to 1000 μm.

(Moisture-Proof Layer) In the present invention, if necessary, the heat-insulating layer may be provided on the front surface, the back surface, or both the front and back surfaces.
It is also preferable to further form a moisture-proof layer in order to prevent moisture from penetrating into the heat-insulating decorative sheet or the heat-insulating member. Here, the back surface refers to the surface of the heat insulating layer opposite to the decorative layer.

As such a moisture-proof layer, for example, a polyolefin resin such as polyethylene (high-density, medium-density or high-density), polypropylene, or polymethylpentene (having a moisture permeation resistance value of 390 m2hmmHg at a thickness of 100 μm)
/ G), a resin material having high moisture permeability such as biaxially stretched polyethylene terephthalate, polyvinyl chloride, or polyvinylidene chloride, preferably having a moisture permeability resistance of 50 m
It is preferable to be made of a material of 2 hmmHg / g or more. Further, the thickness of the moisture-proof layer is usually preferably about 20 to 100 μm.

Further, a moisture-proof layer made of aluminum, silica, or the like is provided on the front surface, the back surface, or the front and back surfaces of the heat-insulating layer by a vacuum evaporation method or a CVD (Chemical Vapor Depth).
formation method, a sputtering method, or the like. Alternatively, a moisture-proof layer (for example, a biaxially-stretched polyethylene terephthalate sheet on which silica is deposited) made of a laminate of the above resin layer and a metal layer or a metal oxide layer can be used.

(Cosmetic Layer) The decorative sheet of the present invention is provided on the heat-insulating layer directly or via another layer such as the moisture-proof layer.
A decorative layer is laminated. The decorative layer is made of polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer as the base layer. , Polyolefin-based resins such as olefin-based thermoplastic elastomers, poly (methyl) methacrylate, poly (meth) ethyl acrylate, poly (meth) butyl acrylate, ethyl (meth) acrylate-butyl (meth) acrylate Polymer,
Methyl (meth) acrylate-styrene copolymer, methyl (meth) acrylate-butyl (meth) acrylate-
Acrylic resin such as (meth) acrylic acid-2-hydroxyethyl copolymer (herein, (meth) acryl means acryl or methacryl), polyethylene terephthalate, polybutylene terephthalate, ethylene-terephthalate-iso Polyester resins such as phthalate copolymers, polyester thermoplastic elastomers, polyvinyl chloride, polyvinylidene chloride, nylon,
Resins such as ABS (acrylonitrile-butadiene-styrene copolymer) and polystyrene (the resin is generally a material having high moisture-permeation resistance. In particular, when the moisture-proof property of the base material layer is required, polyethylene, polyvinylidene chloride, etc. It is preferable to select a material having a higher moisture permeability).

Woven or nonwoven fabrics such as inorganic fibers such as glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, and carbon fiber; organic resin fibers such as polyester fiber and vinylon fiber; and cedar, cypress, and oak And a thin plate (a veneer) of a tree such as oak. In addition to these single layers, a laminate of two or more layers can be used as the base material layer.

The substrate layer is usually about 20 to 200 μm in thickness, and can be used as it is when the substrate itself has a sufficient design appearance. Usually, the substrate layer is subjected to a decoration treatment.

As the decoration treatment, a pattern layer, a metal thin film layer or the like is formed on the surface of the base material, an uneven pattern is formed on the surface of the base material, or when the base material layer is a resin, a dye, a pigment or the like is used. A colorant may be kneaded or a combination thereof.

Examples of the coloring agent include inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, graphite, carbon black, isoindolinone yellow, Hansa yellow, quinacridone red, and permanent red. Organic pigments (or dyes) such as 4R, phthalocyanine blue, indathrene blue RS, and aniline black; metal pigments (or dyes) made of foil powder such as aluminum and brass; titanium dioxide-coated mica;
There are pearlescent (pearl) pigments made of foil powder such as basic lead carbonate. These are added and dispersed as powder or flaky foil pieces.

The picture layer is formed with a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, etc., using ink (or dye) to form a picture (pattern).

The pattern includes a wood pattern, a stone pattern, a cloth pattern, a squeezed pattern, a geometric figure, a character, a symbol, and a solid image.

As the ink (or) paint, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester resins, urethane resins, acrylic resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers are used as binders. Using a cellulose resin or the like, it is possible to use one or a mixture of two or more of these, to which a known coloring agent as described above is added.

The uneven pattern is typically formed by embossing, particularly in the case of a thermoplastic resin substrate layer, but other methods such as hairline processing are also possible. In embossing, the base material layer is heated and softened, pressurized and shaped with an embossing plate, and fixed by cooling. A known sheet-fed or rotary embossing machine is used.

As the embossed pattern, there are a wood grain conduit groove, a rugged surface of a slab (such as a granite cleavage surface), a cloth surface texture, a matte finish, a grain, a hairline, a parallel groove, a brickwork or a tiled joint groove, and the like.

Further, if necessary, the concave portions of the concavo-convex pattern can be filled with a coloring ink by a known wiping method (see Japanese Patent Publication No. 58-14312). As the coloring ink, the same one as described above can be used. However, from the viewpoint of abrasion resistance, a material using a two-component curable urethane resin as a binder is preferable.

The metal thin film is made of aluminum, chromium, gold,
Using a metal such as silver or copper, a film can be formed and formed by a method such as a vacuum evaporation method or a sputtering method. The metal thin film may be provided on the entire surface, or may be provided partially, for example, in a pattern.

Further, in the decorative sheet of the present invention,
If necessary, a surface protective layer for surface protection or decoration treatment can be formed on the picture layer. The surface protective layer can be formed of, for example, a breathable acrylic resin or nonwoven fabric. Further, the surface protective layer may be formed of a laminate including a plurality of layers.

In order to impart weather resistance (light), the base layer, the picture layer or the surface protective layer may be formed of benzotriazole, benzophenone, cyanoacrylate, or the like.
Various ultraviolet absorbers such as fine particle cerium oxide and fine particle zinc oxide, and / or light stabilizers such as hindered amine radical scavengers can also be added.

Examples of the decorative layer having good design appearance, weather resistance and suitability for bending are, for example, a colored acrylic resin sheet which has been subjected to decorative treatment in order from the side closer to the heat insulating layer. Examples thereof include those obtained by laminating transparent acrylic resin sheets having an elongation at break of 100% or more according to JIS-K7127.

The coloring of the colored acrylic resin sheet may be either transparent coloring or opaque coloring. As the acrylic resin to be used, it is preferable to use the same one as a transparent acrylic resin sheet described later in terms of bending workability,
Ordinary acrylic resins such as those listed above may be used.
This is because the suitability of the entire decorative layer for bending can be ensured by the transparent acrylic resin sheet on the surface at least.
For coloring, it is preferable to add a predetermined amount of a colorant such as a weather-resistant paint or pigment. The thickness is 20 to 150 μm
Degree. The colorant may be selected from those listed above.

The transparent acrylic resin sheet is made of JIS-
Elongation at break (tensile fracture elongation) of K7127 is 10
It is characteristic that it is 0% or more. That is, by improving the elongation at break of the transparent acrylic resin sheet at room temperature such as V-cut processing and lapping processing, or impact resistance at the time of molding processing at a low temperature (less than the softening temperature of the sheet), It is intended to improve crack resistance. The transparent material may be colorless and transparent or matte and transparent.

Here, the elongation at break in JIS-K7127 means elongation at break at a tensile test speed of 50 mm / min using a No. 4 type test piece. Generally, the elongation at break increases as the glass transition point of the resin decreases.
Therefore, it is preferable to use an acrylic resin having a low glass transition point for the transparent acrylic resin sheet of the present invention. Generally, the lower the degree of polymerization, the lower the glass transition temperature. Even with the same acrylic resin, poly (butyl meth) acrylate has a lower glass transition temperature than poly (methyl meth) acrylate. Further, the glass transition temperature of the copolymer is lower than that of the homopolymer of the alkyl (meth) acrylate. However, when a resin having a glass transition point that is too low is used, blocking (a phenomenon in which the front and back surfaces of the sheet stick to each other) tends to easily occur in the winding step of the resin sheet.

If necessary, the acrylic resin sheet may contain, for example, acrylic rubber (butyl acrylate-acrylonitrile copolymer), hydrogenated diene rubber, or the like as long as weather resistance and transparency are not impaired. Rubber having high weather resistance and high transparency can be added. By this addition, the elongation at break of the transparent acrylic resin sheet can be increased, and impact resistance can be imparted to the sheet. The addition amount is usually 5% by weight or less, but can be appropriately adjusted according to the performance required for the decorative sheet.

Further, an inorganic filler composed of particles of calcium carbonate, clay, alumina, talc and the like, a matting agent composed of particles of silica and the like can be added to the acrylic resin. The addition amount is about 1 to 60 parts by weight, more preferably about 1 to 30 parts by weight.

Further, various additives, reinforcing materials, and fillers such as a flame retardant, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, etc. may be added to the colored acrylic resin and the transparent acrylic resin. Can be added.

The flame retardant is added for imparting flame resistance to the decorative sheet. Examples thereof include paraffin chloride, tricresyl phosphate, chlorinated oil, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, and tetrabromophthalic anhydride. Bromobisphenol A, dibromopropyl phosphate, tri (2,3-dibromopropyl) phosphate,
Examples include antimony oxide, hydrated alumina, and barium borate.

Antioxidants are added to suppress oxidative decomposition of the decorative sheet resin, and include, for example, alkylphenols, amines, quinones and the like.

The UV absorber and the light stabilizer are added for the purpose of imparting better weather resistance (light resistance) to the resin, and the amount of the UV absorber and the light stabilizer is usually 0.1%.
About 1 to 5% by weight is preferable.

Examples of the ultraviolet absorber include various ultraviolet absorbers such as benzophenone, salicylate, benzotriazole, and acrylonitrile. As a particularly preferred example, an organic compound having a hydroxyl group in the molecule can be used from the viewpoint of transparency to visible light.

For example, 2- (2′-hydroxy-3 ′,
5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t
tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-amyl-5′-isobutylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′ -Isobutyl-5'-propylphenyl) -5'-chlorobenzotriazole and other 2'-hydroxyphenyl-5-chlorobenzotriazole ultraviolet absorbers, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and the like Hydroxy such as 2'-hydroxyphenylbenzotriazole ultraviolet absorber, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, etc. Benzophenone UV absorber, phenol salicylate, 4-tert-butyl It can be exemplified salicylic acid ester ultraviolet absorbers such as phenyl salicylate.

In addition, a reactive ultraviolet absorber having an acryloyl group or a methacryloyl group introduced into a benzotriazole skeleton can be used. In addition, a particle size of 0.2
Inorganic substances such as zinc oxide, cerium oxide, and titanium oxide having a size of μm or less can also be used. Of these, the use of a benzotriazole-based ultraviolet absorber is particularly preferable in consideration of the problems of the absorption wavelength and the coloring property.

As a light stabilizer, bis- (2,2,6,
Radical scavengers such as hindered amine radical scavengers such as 6-tetramethyl-4-piperidinyl) sebacate and piperidine radical scavengers can be used.

If necessary, the surface or both surfaces of the colored acrylic resin sheet and the transparent acrylic resin sheet may be subjected to corona discharge treatment, plasma treatment, primer (also referred to as anchor) coating treatment, ozone treatment, and acid treatment. A known easy adhesion treatment such as a degreasing treatment, a surface roughening treatment, an activation treatment with a chemical such as cupric chloride or the like can be performed.

In the present invention, a decoration treatment is performed on the colored acrylic resin sheet. As the decoration processing, the same processing as the above-described processing can be employed. However, as a binder used for the ink or paint used for the decoration treatment, for example, a vinyl chloride-vinyl acetate copolymer, an acrylic resin, or a mixed system thereof can be used.
When mixing both, acrylic resin / vinyl chloride
The vinyl acetate copolymer is preferably in the range of 1/9 to 9/1.

In particular, from the viewpoints of weather resistance, printability and bending, the acrylic resin / vinyl chloride-vinyl acetate copolymer is preferably in the range of 6/4 to 9/1.

The vinyl acetate content in the vinyl chloride-vinyl acetate copolymer is about 1 to 20% by weight, and the average degree of polymerization is 4%.
It is about 00 to 900, and if necessary, a copolymer of a monomer having a carboxyl group or a hydroxyl group such as maleic acid or vinyl alcohol may be used.

The acrylic resin used is the same as described above. When both are mixed, since the acrylic resin sheet is an acrylic film, the organic solvent resistance is poor and the sheet easily swells or dissolves. Not preferred. In addition, those obtained by adding the above-listed pigments are used.

(Heat Insulating Decorative Sheet) FIGS. 1 and 2 show examples of the heat insulating decorative sheet of the present invention. FIG. 1A shows the resin b
Thermal insulation layer 1 made of cellular resin having many bubbles a in it
FIG. 3 is a structural cross-sectional view of a decorative sheet 10A having a structure in which a decorative layer 2 made of a base resin containing a pigment c is laminated thereon;
(B) shows a base material layer 3 on a heat insulating layer 1 made of a cellular resin.
FIG. 2C is a structural cross-sectional view of a decorative sheet 10B having a structure in which a decorative layer 2 composed of a pattern layer 4 and a decorative layer 2 are laminated. FIG. 4C is a substrate in which an embossed pattern d is formed on the surface on a heat insulating layer 1 composed of a cellular resin. FIG. 3 is a structural cross-sectional view of a decorative sheet 10 </ b> C having a structure in which a decorative layer 2 including a layer 3 is laminated via an adhesive layer 12.

FIG. 2 (D) shows that after embossing the surface on the heat insulating layer 1 made of cellular resin, the embossed concave portion formed by the embossing is filled with the coloring ink e, and the surface is further embossed. It is a structural cross section of the decorative sheet 10D of the structure which laminated | stacked the base material layer 3 which has the decorative layer 2 in which the picture layer 4 was provided via the adhesive layer 12, (E) is a heat insulation layer which consists of a cellular resin. 1 on the moisture-proof layer 5 via an adhesive layer 13
Is a structural cross-sectional view of a decorative sheet 10E having a structure in which a decorative layer 2 made of a base resin containing a pigment c is laminated on the moisture-proof layer 5 with an adhesive layer 12 interposed therebetween. A decorative layer 2 having a pattern layer 4 provided on a base material layer 2 is laminated on an insulating layer 1 made of a resin in the form of an adhesive layer 12, and further,
FIG. 3 is a structural cross-sectional view of a decorative sheet 10F having a structure in which a moisture-proof layer 5 is formed on the back surface of a heat insulating layer 1 with an adhesive layer 13 interposed therebetween.

It should be noted that what has been described above is merely an embodiment of the decorative sheet of the present invention, and it goes without saying that the layer structure can be changed without departing from the spirit of the present invention.

(Manufacture of Insulated Decorative Sheet) Next, a general method of manufacturing a heat-insulated decorative sheet of the present invention will be described with reference to the decorative sheets shown in FIGS. 1 and 2 as an example.

The decorative sheet shown in FIG. 1A can be manufactured, for example, as follows. First, a base sheet constituting the decorative layer 2 colored with the pigment c is prepared, and if necessary, one side (the side on which the heat insulating layer is formed) or both sides of the base sheet is easily adhered by corona discharge treatment or the like. Perform processing.

Next, a solution obtained by dissolving a resin composition in which a foaming agent is blended in a predetermined ratio in a resin b listed as a material that can be used as the heat insulating layer, or a solution obtained by dissolving the resin in water, or A composition obtained by blending a foaming agent in a predetermined ratio with the resin emulsion prepared above is coated on a base sheet at a predetermined coating amount using a coating machine such as a roll coater, a comma coater, or a curtain floater, and then dried and solidified. At first, a heat-insulating layer 1 made of a cellular resin is formed by heating and foaming the coating film to form a coating film.
(A) The decorative sheet 10A can be obtained.

Further, the decorative sheet 10B shown in FIG.
First, a base sheet provided with a decorative layer 2 having a picture layer 4 by a gravure printing method is prepared, and if necessary, one side (the side on which the heat insulating layer is formed) or both sides of the base sheet is subjected to corona discharge treatment. And the like. Next, on the back surface (non-printing surface) side of the base sheet, a resin composition containing a predetermined amount of a foaming agent is melt-extruded and coated from a T-die, laminated, foamed at the same time, and cooled and solidified.
By forming the heat insulating layer 1 on the back side of the decorative layer 2,
Can be manufactured.

First, the decorative sheet 10C shown in FIG.
A base sheet made of a thermoplastic resin is prepared, and a sheet constituting the decorative layer 2 having an embossed pattern d formed on the sheet surface by embossing is obtained. Further, if necessary, one side (the side on which the heat insulating layer is formed) or both sides of the base sheet is subjected to an easy adhesion treatment such as a corona discharge treatment. Separately, a composition in which a foaming agent is blended in a predetermined ratio in resin b is melt-extruded from a T-die to form a film, and at the same time, foamed at a predetermined magnification to obtain a heat insulating layer 1. Next, the heat insulating layer 1 and the non-embossed pattern side of the decorative layer 2 are bonded (dry laminated) via a two-component curable adhesive 12 such as a two-component curable urethane resin therebetween. . In addition, as a method of laminating, there is a method by thermal fusion other than dry lamination, but since thermal fusion easily causes the disappearance of the embossed pattern, it is preferable to laminate using dry lamination.

The decorative sheet 10D shown in FIG.
A base sheet of a thermoplastic resin is prepared, the sheet surface is embossed, the embossed recesses formed by the embossing are filled with wiping ink e, and the surface is subjected to pattern printing 4 by gravure printing. By
A sheet constituting the decorative layer 2 is obtained. If necessary,
One side (the side on which the heat insulating layer is formed) or both sides of the base sheet is subjected to an easy adhesion treatment such as a corona discharge treatment. Then
Using this, it can be manufactured by dry lamination similarly to the decorative sheet shown in FIG. 1 (C).

The decorative sheet 10E shown in FIG.
A base sheet constituting the decorative layer 2 colored by the pigment c is prepared, and if necessary, an easy adhesion treatment such as a corona discharge treatment is performed on one surface (the surface on which the heat insulating layer is formed) or both surfaces of the base sheet. Apply. On the other hand, as in the case of FIG.
A separately manufactured heat insulating layer 1 is obtained.

Next, on the heat insulating layer 1, a moisture-proof material is formed by previously laminating a metal or metal oxide such as aluminum or silica on a biaxially stretched polyethylene terephthalate sheet by vacuum deposition, CVD, sputtering or the like. The layer 5 is formed by lamination by dry lamination. Next, the heat insulating layer 1 and the decorative layer 2 can be laminated on the moisture-proof layer 5 by a dry laminating method in a direction as shown in the drawing.

In this case, it is also preferable to form an easily adhesive layer such as a primer layer between the decorative layer 2 and the moisture-proof layer 5 and between the moisture-proof layer 5 and the heat insulating layer 1 before dry lamination. .

As for the decorative sheet 10F shown in FIG. 2F, first, a base sheet constituting the decorative layer 2 having the picture layer 4 is prepared in the same manner as in the case of FIG. One side (the side on which the heat insulating layer is formed) or both sides of the base sheet is subjected to an easy adhesion treatment such as a corona discharge treatment. Next, the resins b listed as being usable as the heat insulating layer
In FIG. 1, a resin composition containing a predetermined amount of a foaming agent was added.
As in the case of (C), a film is formed by melt extrusion and foamed to form a heat insulating layer 1 made of a cellular resin.

Then, on the back side of the heat insulating layer 1, FIG.
It can be manufactured by forming the moisture-proof layer 5 using the same material and method as in the case of (E).

(Heat-Insulating Decorative Member) The heat-insulating decorative sheet of the present invention obtained as described above is adhered to a desired substrate directly or via another layer to form a heat-insulating decorative member of the present invention. be able to. Also, by pasting directly or via another layer on the already installed base material,
The substrate may be provided with a heat insulating effect and a surface decoration effect. Examples of the other layer include an adhesive layer.

The member used for the heat insulating member of the present invention has a shape such as a hollow or solid flat plate, a plate such as a curved curved plate, a prism such as a cylinder or a polygonal prism. Various materials such as metal, wood, resin, and ceramics are used as the material of the base material. However, the effect of improving the heat insulating property by laminating the decorative sheet of the present invention on a substrate is generally a metal having a high thermal conductivity itself. Examples of the metal include iron, carbon steel, iron alloys such as stainless steel, aluminum, aluminum alloys such as duralumin, copper, brass, and titanium.

FIG. 3 shows an example of the heat insulating member of the present invention. FIG.
(A) is a heat insulating decorative sheet 10 shown in FIG.
FIG. 6 is a structural cross-sectional view of a heat insulating member 11A in which a plate-shaped metal base 7 is provided on the moistureproof layer 5 side of F with an adhesive layer 6 interposed therebetween. FIG. 3B shows a hollow polygonal column,
One surface thereof is cut along the axial direction to form an opening f on the surface side (outside) of the metal base 7 via an adhesive layer 6 on the surface of the grain pattern layer 4 (decorative layer) 2) and a heat insulating decorative sheet 10G below the decorative layer 2 having a heat insulating layer 1 made of a cellular resin having a number of bubbles a in a resin b.
It is a perspective view of the heat insulation member 11B on which was laminated. FIG.
As a method for laminating a heat insulating decorative sheet on a plurality of side surfaces of a polygonal columnar base material such as the metal base material 7 of (B),
The lapping process disclosed in Japanese Patent Publication No. 61-5895 and the like is typical. In addition, the vacuum press method disclosed in Japanese Patent Publication No. 60-58014 and the like,
The V-cut processing method disclosed in Japanese Unexamined Patent Application Publication No. 2000-163, etc. can also be applied.

These heat insulating members 11A and 11B are
For example, after the entire surface of the metal substrate 7 is coated with the adhesive 6, the decorative sheet 10 </ b> F or 10 </ b> G of the present invention is attached to the back surface of the decorative sheet (the side not having the decorative layer 2). It can be manufactured by doing.

The adhesive that can be used is not particularly limited as long as it can bond the metal substrate and the decorative sheet. For example, a two-component (reaction) -curable adhesive such as a two-component curable urethane resin or a two-component curable epoxy resin, a thermosetting adhesive such as a thermosetting polyester or a phenolic resin, or polyacetic acid. Examples include thermoplastic adhesives such as vinyl-based, acrylic resin-based, and polyethylene-based adhesives.

The decorative heat insulating sheet and the heat insulating member of the present invention are used as various interior materials or exterior materials. For example, roofs, exterior walls, door pockets, window frames, roof decks, balconies, fences, gates, door frames, and other building or exterior members of fittings, rims, skirting boards, handrails, interior doors, interior walls, partitions, etc. Examples include interior members such as members or fittings, vehicle exterior materials, vehicle interior materials, and the like.

[0086]

Next, the present invention will be described in detail with reference to examples.

Example 1 First, a transparent biaxially stretched polypropylene film 3 ′ having a thickness of 25 μm was prepared, and both sides of the film 3 ′ were subjected to corona discharge treatment. Next, a sheet having a pattern layer 4 'formed as a decorative layer on the surface of the film 3' was obtained.
The pattern layer 4 ′ is formed by the first rotatable multicolor printing method.
A yellowish-brown ink (a two-component curable urethane resin in which 8 parts by weight of 1,6-hexamethylene diisocyanate is added as a crosslinking agent to 100 parts by weight of a main component of an acrylic polyol as a binder, and carbon black as a pigment The whole solid printing layer 4′a is printed using a red, black, white and black ink (the binder is the same as the first color and the pigment is carbon black). And a pattern with a petal pattern added thereto) to form a wood pattern 4′b of cedar planks.

Next, the basis weight of 25 was applied to the surface of the obtained sheet.
g / cm ^{2 of} an acrylic dry nonwoven fabric (manufactured by Nippon Viclean Co., Ltd., product number OL-4063), heat-softened them, pressurized and cooled with a metal embossing plate, and melted both. At the same time, the recoat layer 8 was formed by forming an uneven pattern of the wood channel conduit grooves on the nonwoven fabric surface. Further, in order to impart weather resistance thereon, an acrylic resin-based coating agent was surface-coated by a roll coating method to form a surface protective layer 9, thereby forming a decorative layer.

Further, on the back surface of the film 3 ′ of the decorative layer, as a heat insulating layer, a polypropylene resin composition obtained by injecting butane gas into molten polypropylene was applied in an amount of 40 g /.
It was melt-extruded with an application amount of m ² and foamed at the same time to form a heat insulating layer 1 ′ made of a cellular resin having a large number of bubbles a in a resin b made of polypropylene. The layer thickness of the heat insulating layer 1 'is 2 mm, and the expansion ratio (layer thickness after foaming /
The layer thickness before foaming) was 30 times.

Further, a biaxially stretched PET (polyethylene terephthalate) film having a thickness of 50 μm on which aluminum was vapor-deposited at 400 ° as a moisture-proof layer 5 ′ was added to the two-component curable acrylic urethane-based adhesive 6 a (acrylic polyol). 4 g / m ² of the main agent mixed with a crosslinking agent of tolylene diisocyanate).
A heat insulating decorative sheet 10H of the present example having the structure shown in FIG.

Example 2 In Example 1, melt-extrusion was performed at a coating amount of 60 g / m ² , and a cellular resin of polypropylene having an expansion ratio of 20 was used as a heat insulating layer (others are the same as in Example 1). Example insulation decorative sheets were obtained.

Example 3 In Example 1, melt-extrusion was performed at a coating amount of 100 g / m ² , and a cellular resin made of polypropylene with an expansion ratio of 10 was used as a heat insulating layer (others are the same as in Example 1). Example insulation decorative sheets were obtained.

Example 4 A heat insulating decorative sheet of this example was obtained in the same manner as in Example 1 except that the following was used as the decorative layer. That is, a colored methacrylate resin sheet (thickness 80 μm)
m, manufactured by Kyowa Leather Co., Ltd.) On the surface, a mixture of vinyl chloride-vinyl acetate copolymer / acrylic resin = 2/8 (weight ratio) was used as a binder, and red petals, isoindolinone yellow, titanium white, and carbon black were used. The decoration processing was performed by printing a wood grain pattern by a gravure printing method using an ink containing a pigment mainly composed of.

Next, a transparent acrylic resin sheet (thickness of 50%) having an elongation at break of 110% according to JIS-K7127 (No. 4 test piece, test speed 50 mm / min, the same applies hereinafter)
μm) by heating and softening, pressing with an embossing plate roll,
At the same time as doubling by a hot press method, a concave and convex pattern of a conduit groove is formed on the transparent acrylic resin sheet, and a wiping ink using a two-part curable urethane resin of acrylic polyol and hexamethylene diisocyanate as a binder and carbon black as a pigment Then, the wiping ink was filled in the concave portions of the uneven pattern.

Further, a decorative layer was formed by forming an overcoating protective layer on the sheet surface with a two-component curable fluororesin composed of a fluorocarbon resin having a hydroxyl group in the molecule and a crosslinking agent of hexamethylene diisocyanate.

Example 5 A heat insulating decorative sheet of this example was obtained in the same manner as in Example 1 except that the following was used as the decorative layer. Specifically, a mixture of vinyl chloride-vinyl acetate copolymer / acrylic resin = 2/8 (weight ratio) was used as a binder on the surface of a colored methacrylic acid ester resin sheet (thickness: 80 μm, manufactured by Kyowa Leather Co., Ltd.). A decoration process was performed by printing a wood grain pattern by a gravure printing method using an ink containing a pigment mainly composed of isoindolinone yellow, titanium white, and carbon black.

Next, a transparent acrylic resin sheet having a breaking elongation of 120% (thickness: 50 μm, Mitsubishi Rayon Co., Ltd.)
Was softened by heating, pressed with an embossing plate roll, and doubling was performed by a hot press method. Simultaneously, a concave and convex pattern of a conduit groove was formed on the transparent acrylic resin sheet to obtain a decorative layer.

Example 6 In Example 4, as a heat insulating layer, a polypropylene resin composition obtained by injecting butane gas into molten polypropylene was melt-extruded at an application amount of 60 g / m ² , and immediately thereafter, an electron beam was irradiated with 3 Mrad. It was made to foam while cross-linking and used as a cellular resin layer of polypropylene having an expansion ratio of 20 times. Except for the above, it was the same as Example 4.

Comparative Example 1 In Example 1, the heat insulating layer was made of a heat insulating paint composed of 50% by weight of hollow glass beads and 50% by weight of an acrylic resin binder (Nagashima Special Paint Co., Ltd., trade name: Suncoat Thermoshield). Was formed by applying and drying by a roll coating method so as to have a thickness of 0.01 mm, and a heat insulating decorative sheet of a comparative example was produced in the same manner as in Example 1.

Comparative Example 2 In Example 1, the heat-insulating layer was composed of 50% by weight of hollow glass beads and 50% by weight of an acrylic resin binder (Nagashima Special Paint Co., Ltd., trade name: Suncoat Thermoshield). Was applied by a roll coating method so as to have a thickness of 2 mm, but the drying was slow and processing by a coating machine was difficult. In addition, since the film was thick, cracking occurred when it was bent.

Comparative Example 3 A heat insulating decorative sheet of this comparative example was obtained in the same manner as in Example 1, except that the following decorative layer was used. That is, on the surface of a colored methacrylate resin sheet (80 μm thick, manufactured by Kyowa Leather Co., Ltd.), vinyl chloride-vinyl acetate /
Using a mixture of acrylic resin = 2/8 (weight ratio) as a binder, and printing a wood grain pattern by gravure printing using an ink containing a pigment consisting mainly of reddish pattern, isoindolinone yellow, titanium white, and carbon black By doing
Decoration treatment was applied.

Next, an elongation at break of 4 was printed on the printed sheet.
A 0% transparent acrylic resin sheet (thickness: 50 μm, manufactured by Mitsubishi Rayon Co., Ltd.) is heated and softened, pressed with an embossing plate roll and heat-fused, and at the same time, the irregularities of the conduit grooves are formed on the surface of the transparent acrylic resin sheet. To give a decorative layer.

Comparative Example 4 In Example 1, the resin was melt-extruded at a coating amount of 220 g / m ² , and a cellular resin of polypropylene having an expansion ratio of 5 was used as a heat insulating layer (others are the same as in Example 1). Example insulation decorative sheets were obtained.

Bending workability test The heat-insulating decorative sheet 10H obtained in Examples 1 to 6 and Comparative Examples 1 to 4 was applied to the surface of the substrate 7 'with an acrylic adhesive (a main component of acrylic polyol). Mixing a crosslinking agent of tolylene diisocyanate, coating amount: 20 g /
m ² ) 6b to form a heat insulating member 11C of this example having the structure shown in FIG. 4B. Here, the substrate 7 '
Is an aluminum substrate having a hollow shape and a thickness of 1 mm as shown in FIG. 3 (B), and the above-mentioned heat insulating decorative sheet 10H was laminated by using a lapping method. In the heat insulating member, in Examples 1 to 6 and Comparative Examples 1 and 4, the heat insulating decorative sheet follows and adheres to the corners of the substrate 7 ′, and cracks (along with the decorative layer and the heat insulating layer). Crack)
No whitening of the sheet occurred. On the other hand, in Comparative Examples 2 and 3, cracks occurred in the decorative layer at the corners of the substrate 7 '.

Insulation Effect Test of Decorative Member The heat- insulating decorative sheets obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were subjected to a room temperature of 10 ° C. and a relative humidity of 30% R.
In the room H, floated on ice water at 0 ° C. As a result, in the decorative sheets of Example 1, Example 4, Example 5, Comparative Example 2 and Comparative Example 3, the surface temperature of the decorative sheet was 7 ° C.
The surface temperature of the decorative sheets of Example 2 and Example 6 was 6 ° C., and the surface temperature of the decorative sheet of Example 3 was 5 ° C. No dew condensation occurred on the surface. On the other hand, the surface temperature of the decorative sheet of Comparative Example 1 was 1 ° C., and the surface temperature of the decorative sheet of Comparative Example 4 was 2 ° C., and dew condensation occurred on the surface.

[0106] Using the adiabatic decorative sheet weathering test above embodiment obtained in the manner of 1, 4, 5, 6 and Comparative Example 3, the sunshine carbon arc燈型Weather-O Meter, black panel temperature 63 ° C. , Under the conditions of rain for 18 minutes for 120 minutes,
Irradiate artificial light including ultraviolet light for up to 4,000 hours,
The degree of surface deterioration of each of the heat-insulating decorative sheets after lapse of 4,000 hours and 4,000 hours, and whether or not peeling was observed between the layers of the heat-insulating decorative sheets were visually observed.
At the same time, after 2,000 hours and 4,000 hours
After the lapse of time, each of the heat insulating decorative sheets was taken out and subjected to V-cut processing (20 ° C.), and it was examined whether or not whitening, cracks, breakage, etc. were observed in each of the heat insulating decorative sheets. The test results are shown in Table 1 below.

[0107]

[Table 1]

As a result, in each of the heat insulating decorative sheets of Examples 4, 5, and 6 and Comparative Example 3, no deterioration was observed on the surface even after 4,000 hours had elapsed, and no delamination occurred. Also, even when the V-cut processing was performed, no whitening, cracks, or breaks were found in the heat insulating decorative sheet. On the other hand, in the heat insulating decorative sheet of Example 1, there was no change at the lapse of 2,000 hours, but after 4000 hours, the interlayer between the polypropylene film 3 ′ and the acrylic dry nonwoven fabric was partially peeled off at the end. I was

[0109]

As described above, the heat-insulating decorative sheet and heat-insulating member of the present invention are stable against indoor and outdoor temperature changes.

Therefore, when the interior of the room to which the heat insulating decorative sheet and the heat insulating member of the present invention are applied is cooled or heated in summer or winter, an excellent heat retaining effect and an energy saving effect can be obtained. Also, especially when heating indoors in winter,
When the external temperature drops, no dew condensation occurs inside.

In particular, when the moisture-proof layer is provided on one side or both sides of the heat-insulating layer in the heat-insulating decorative sheet and the heat-insulating member of the present invention, excellent moisture-proofing effect is obtained in addition to the above-mentioned heat retaining effect. The effect can be obtained.

[Brief description of the drawings]

FIG. 1 is a structural sectional view of a heat insulating decorative sheet of the present invention.

FIG. 2 is a structural cross-sectional view of the heat insulating decorative sheet of the present invention.

FIG. 3 is a structural sectional view of the heat insulating member of the present invention.

FIG. 4 is a structural cross-sectional view of a heat insulating decorative sheet (A) of Example 1 and a heat insulating member (B) of Example 6.

[Explanation of symbols]

1, 1 ': heat insulating layer, 2, 2': decorative layer, 3, 3 ': base material layer, 4, 4': picture layer, 5, 5 ': moisture-proof layer, 6, 6' ...
Adhesive layer, 7, 7 ': metal substrate, 8: recoat layer, 9:
Surface protective layer, a: air bubbles, b: resin binder, c: colored pigment, d: embossed pattern, e: colored ink (wiping ink), f: opening, 10A, 10B, 10C, 10
D, 10E, 10F, 10G ... heat insulating decorative sheet, 11
A, 11B, 11C ... heat insulating members.

Claims (5)

[Claims] 1. A heat insulating decorative sheet comprising a heat insulating layer made of a cellular resin and a decorative layer provided on the heat insulating layer. 2. The heat insulating decorative sheet according to claim 1, wherein the expansion ratio of the heat insulating layer is 10 times or more. 3. The decorative layer is formed by laminating a transparent acrylic resin sheet having an elongation at break of 100% or more according to JIS-K7127 on a colored acrylic resin sheet subjected to a decoration treatment. The heat insulating decorative sheet according to 1 or 2. 4. The heat-insulating decorative sheet according to claim 1, further comprising a moisture-proof layer on the back side, the front side, or both sides of the heat insulating layer. 5. A heat insulating member, comprising a base material provided directly or via another layer on the back side of the heat insulating decorative sheet according to claim 1, 2, 3 or 4.