JP6065709B2 - Cosmetic sheet and cosmetic material - Google Patents

Description

  The present invention relates to a decorative sheet and a decorative material.

  When a decorative sheet is used for floors, joinery, stairs, etc., it can reduce energy consumption during cooling and heating due to its excellent heat retention effect against external temperature changes, and induces stroke, myocardial infarction, etc. From the standpoint that the risk of heat shock (the effect of the body on sudden temperature changes) can be reduced, the decorative sheet is required to have heat insulation. Conventionally, as a method for imparting heat insulation to a decorative sheet, it is known that a heat insulating layer containing hollow beads and a binder resin is formed on the back side of the decorative layer, and this is used as a decorative sheet (Patent Document 1). .

  However, the decorative sheet having the heat insulating layer is easy to pick up unevenness due to the adherend when the adhering material such as a wooden substrate is formed on the back side of the decorative sheet to obtain the decorative material (that is, There is a problem that the front surface of the decorative sheet easily picks up the unevenness of the adherend. Further, if the content of the hollow beads is too large, physical properties such as scratch resistance are deteriorated, and if the content of the hollow beads is too small, a sufficient heat insulating effect cannot be obtained.

  As a method for improving such a problem, it is known that a heat insulating layer (heat insulating foam layer) obtained by foaming a binder resin is formed on the back side of the decorative layer, and this is used as a decorative sheet (Patent Document 2). . According to this heat insulating foam layer, the problem of unevenness can be solved while imparting heat insulation to the decorative sheet.

  However, a decorative sheet having a heat insulating foam layer has a problem that caster resistance is lowered, and also has a problem that the heat insulation, scratch resistance, and the like are lowered depending on the thickness (layer thickness) of the heat insulating foam layer.

JP 2000-158603 A JP 2000-296573 A

  Therefore, in order to obtain excellent heat insulation, scratch resistance and caster resistance while eliminating the problem of unevenness, a heat insulation layer containing hollow beads and a binder resin and a foam heat insulation layer obtained by foaming the binder resin are used in combination. A way to do this is conceivable.

  However, when there is a temperature difference (temperature difference), the resin expands and contracts, but depending on the thickness of the heat insulating layer, the degree of expansion and contraction varies greatly between the heat insulating layer and the foamed heat insulating layer. Therefore, there is a problem that the foamed heat insulating layer in contact with the heat insulating layer causes cohesive failure.

  Therefore, the present invention eliminates the problem of unevenness due to the adherend, and the problem of cohesive failure of the heat insulation layer due to the temperature difference, and a decorative sheet excellent in heat insulation, scratch resistance and caster resistance, An object is to provide a cosmetic material.

  As a result of intensive research to achieve the above object, the present inventor has laminated two different layers having specific physical properties in order on the back side of the decorative layer, and further has a specific amount of hollow beads in the one layer. In the case of inclusion, the present inventors have found that the above object can be achieved, and have completed the present invention.

That is, the present invention relates to the following decorative sheet and decorative material.
1. A decorative sheet in which a synthetic resin backer layer and a foamed resin backer layer are sequentially laminated on the back side of the decorative layer,
(1) The synthetic resin backer layer contains hollow beads,
(2) The content of the hollow beads is 10 to 40 parts by mass with respect to 100 parts by mass of the resin component constituting the synthetic resin backer layer,
(3) The synthetic resin backer layer has a thickness of 200 to 600 μm,
(4) The foamed resin backer layer has a thickness of 200 to 1000 μm,
(5) A decorative sheet, wherein the foamed resin backer layer has an apparent density of 100 to 400 kg / m ³ .
2. The decorative sheet according to item 1, wherein the cell structure of the foamed resin backer layer is a closed cell structure.
3. The decorative sheet according to item 1 or 2, wherein the synthetic resin backer layer is laminated on the foamed resin backer layer via an adhesive.
4. The synthetic resin backer layer and the foamed resin backer layer or the foaming agent-containing resin layer for forming the foamed resin backer layer are co-extruded by a multilayer extruder, Makeup sheet.
5. The makeup according to any one of Items 1 to 4, wherein the decorative layer is a decorative intermediate sheet, decorative paper, melamine plate, or veneer in which one or two or more resin layers are laminated on a base sheet. Sheet.
6. A decorative material obtained by laminating the decorative sheet according to any one of items 1 to 5 on an adherend.

  Hereinafter, the decorative sheet and the decorative material of the present invention will be described.

≪Makeup sheet≫
The decorative sheet of the present invention is a decorative sheet in which a synthetic resin backer layer and a foamed resin backer layer are sequentially laminated on the back side of the decorative layer,
(1) The synthetic resin backer layer contains hollow beads,
(2) The content of the hollow beads is 10 to 40 parts by mass with respect to 100 parts by mass of the resin component constituting the synthetic resin backer layer,
(3) The synthetic resin backer layer has a thickness of 200 to 600 μm,
(4) The foamed resin backer layer has a thickness of 200 to 1000 μm,
(5) The apparent density of the foamed resin backer layer is 100 to 400 kg / m ³ .

  In the decorative sheet of the present invention, two different layers having specific physical properties (that is, a synthetic resin backer layer and a foamed resin backer layer) are sequentially laminated on the back side of the decorative layer, and the synthetic resin backer layer is formed of hollow beads. Is contained in a specific amount. Therefore, the decorative sheet of the present invention has solved the problem of unevenness due to the adherend even when a decorative material is obtained by laminating the adherend such as a wooden substrate, and the temperature difference The problem of cohesive failure of the resulting foamed resin backer layer is also solved. Furthermore, it is excellent in heat insulation, scratch resistance and caster resistance.

  As a layer structure of the decorative sheet, a synthetic resin backer layer and a foamed resin backer layer are sequentially laminated on the back side of the decorative layer. That is, there is no particular limitation as long as the layer configuration condition that the synthetic resin backer layer and the decorative layer are sequentially laminated on the foamed resin backer layer is satisfied. Hereinafter, each layer will be described by taking the layer configuration as an example. In the decorative sheet of the present invention, the decorative layer is a so-called “front surface” (surface visually recognized after construction). Therefore, in this specification, the direction in which the decorative layer is present with respect to the foamed resin backer layer is referred to as “front” or “upper”, and the opposite side is referred to as “back” or “lower”.

Cosmetic layer The layer structure of the decorative layer used in the present invention is not limited, and it is composed of one layer or two or more layers. For example, a decorative sheet, melamine plate, veneer, etc. composed of one layer may be used as a decorative layer, and a decorative sheet intermediate in which one or more resin layers are laminated on a base sheet May be used as a decorative layer. As a decorative sheet intermediate, for example, (1) a decorative sheet having a pattern layer (solid ink layer and / or pattern ink layer), an adhesive layer, a transparent resin layer, a primer layer, and a surface protective layer in this order on a base sheet Sheet intermediate (Note that when the base sheet is a synthetic resin, it is called a so-called doubling specification), (2) So-called single-layer decorative sheet intermediate (a transparent resin layer is not provided in the doubling specification) Any of (decorative sheet) and (3) a so-called back print type decorative sheet intermediate (decorative sheet in which the base sheet is not provided in the decorative sheet of (1)) can be used.

  Hereinafter, the decorative sheet intermediate (decorative layer) of the above (1) will be exemplarily described.

  The base sheet is 1) paper such as thin paper, fine paper, kraft paper, Japanese paper, titanium paper, resin-impregnated paper, inter-paper reinforced paper, etc. 2) wood fiber, glass fiber, asbestos, polyester fiber, vinylon fiber, rayon Examples thereof include one or two or more laminates of woven or non-woven fabric made of fibers and the like, and 3) a synthetic resin sheet such as polyolefin, polyester, polyacryl, polyamide, polyurethane, and polystyrene.

  The thickness of the base sheet is preferably about 20 to 300 μm. The substrate sheet may be colored as necessary. Further, the surface may be subjected to surface treatment such as corona discharge treatment, plasma treatment, or ozone treatment.

  The pattern pattern layer is composed of a pattern ink layer and / or a solid ink layer. The pattern layer can be formed by a printing method such as gravure printing, offset printing, silk screen printing or the like. Examples of the pattern of the pattern ink layer include a wood grain pattern, a stone pattern, a cloth pattern, a skin pattern, a geometric pattern, characters, symbols, line drawings, various abstract patterns, and the like. The solid ink layer is obtained by solid printing of colored ink.

  As the ink of the pattern layer, as a vehicle, chlorinated polyolefin such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane comprising isocyanate and polyol, polyacryl, polyvinyl acetate, polyvinyl chloride, acrylic-urethane copolymer , Vinyl chloride-vinyl acetate copolymer, cellulose resin, polyamide resin, etc. can be used singly or in combination of two or more, and pigments, solvents, various adjuvants, etc. can be added to make them into ink. . Among these, from the viewpoint of environmental problems, adhesion to the printing surface, and the like, one or a mixture of two or more of polyester, polyurethane made of isocyanate and polyol, polyacryl, polyamide-based resin, and the like is preferable.

  The adhesive layer (adhesive layer A) is provided between the pattern layer and the transparent resin layer. The adhesive layer can be obtained, for example, by applying and drying a known dry lamination adhesive such as a two-component curable urethane resin, a urethane type, or a polyester resin type.

  The thickness of the adhesive layer after drying is preferably about 0.1 to 30 μm, more preferably about 1 to 20 μm.

  A transparent resin layer will not be specifically limited if it is a transparent resin layer, For example, it can form suitably with a transparent thermoplastic resin.

  Specifically, soft, semi-rigid or rigid polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer Examples thereof include polymers, ionomers, polyacrylic acid esters, and polymethacrylic acid esters. Among the above, polyolefin resins such as polypropylene are preferable.

  The transparent resin layer may be colored. In this case, a colorant may be added to the thermoplastic resin. As the colorant, pigments or dyes used in the pattern layer can be used.

  For the transparent resin layer, fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, UV absorbers, light stabilizers, radical scavengers, soft components (eg rubber) Various additives such as may be included.

  The transparent resin layer is preferably about 10 to 150 μm, more preferably about 30 to 100 μm.

  The primer layer is provided to improve the adhesion between the transparent resin layer and the surface protective layer. The primer layer is a transparent or translucent layer and can be formed using the resin exemplified as the vehicle of the pattern layer.

  The primer layer is preferably about 0.5 to 20 μm, more preferably about 1 to 5 μm.

  The resin constituting the surface protective layer is preferably a curable resin such as a thermosetting resin or an ionizing radiation curable resin (for example, an electron beam curable resin). In particular, ionizing radiation curable resins are preferable from the viewpoint of high surface hardness, productivity, and the like.

  Examples of thermosetting resins include unsaturated polyester resins, polyurethane resins (including two-component curable polyurethane), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, and melamines. -Urea co-condensation resin, silicon resin, polysiloxane resin and the like.

  A curing agent such as a crosslinking agent and a polymerization initiator, and a polymerization accelerator can be added to the resin. For example, as curing agents, isocyanates, organic sulfonates, etc. can be added to unsaturated polyester resins, polyurethane resins, etc., organic amines, etc. can be added to epoxy resins, peroxides such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc. A radical initiator can be added to the unsaturated polyester resin.

  Examples of the method for forming the surface protective layer with a thermosetting resin include a method in which a solution of a thermosetting resin is applied by a coating method such as a roll coating method or a gravure coating method, followed by drying and curing.

  The ionizing radiation curable resin is not limited as long as it is a resin that undergoes a crosslinking polymerization reaction upon irradiation with ionizing radiation and changes to a three-dimensional polymer structure. For example, one or more prepolymers, oligomers, and monomers having a polymerizable unsaturated bond or epoxy group that can be cross-linked by irradiation with ionizing radiation in the molecule can be used. Examples thereof include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; epoxy resins and the like.

  Examples of the ionizing radiation include visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams, ion beams, etc. Among them, ultraviolet light and / or electron beams are desirable.

  As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used. The wavelength of ultraviolet rays is about 190 to 380 nm.

  As the electron beam source, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The energy of the electron beam is preferably about 100 to 1000 keV, more preferably about 100 to 300 keV. The irradiation amount of the electron beam is preferably about 2 to 15 Mrad.

  The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam, but it is preferable to add a photopolymerization initiator (sensitizer) when it is cured by irradiation with ultraviolet rays.

  Photopolymerization initiators in the case of resin systems having radically polymerizable unsaturated groups include, for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide , Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used. In the case of a resin system having a cationic polymerizable functional group, for example, at least one kind such as an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, and a freeloxysulfoxonium diallyl iodosyl salt. Can be used.

  Although the addition amount of a photoinitiator is not specifically limited, Generally it is about 0.1-10 mass parts with respect to 100 mass parts of ionizing radiation curable resins.

  As a method of forming the surface protective layer with an ionizing radiation curable resin, for example, a solution of an ionizing radiation curable resin may be applied by a coating method such as a gravure coating method or a roll coating method.

  The thickness of the surface protective layer is usually about 0.1 to 50 μm, preferably about 1 to 20 μm.

  In order to further impart scratch resistance and abrasion resistance to the surface protective layer formed from the ionizing radiation curable resin, an inorganic filler may be blended. Examples of inorganic fillers include powdered aluminum oxide, silicon carbide, silicon dioxide, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, Diamond, gold sand, talc, glass fiber and the like can be mentioned.

  The addition amount of the inorganic filler is about 1 to 80 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

  Lamination of each layer constituting the decorative layer is, for example, by forming a pattern layer (solid ink layer, pattern ink layer) on one side of the base sheet by printing, and then forming a two-component curable urethane resin or the like on the pattern layer A transparent resin layer is laminated by a dry lamination method, T-die extrusion method, etc. via a known dry lamination adhesive (transparent adhesive layer), and a transparent surface protective layer is further laminated via a primer layer. It can be done by the method.

  The decorative sheet of the present invention may be embossed from the transparent resin layer side after forming the transparent resin layer. Further, when a surface protective layer is formed on the transparent resin layer, the surface protective layer may be laminated on the transparent resin layer and then embossed from the surface protective layer side. . The concavo-convex pattern formed by embossing can be formed by heating press, hairline processing, or the like. Examples of the uneven pattern include a conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin finish, a grain, a hairline, and a line groove.

  The total thickness of the decorative layer is preferably about 40 to 550 μm, more preferably about 100 to 250 μm.

Synthetic resin backer layer In the present invention, a synthetic resin backer layer (synthetic resin layer) is provided on the back side of the decorative layer. For example, a synthetic resin backer layer is provided on the back surface of the base material sheet (or the back surface of the pattern layer when there is a pattern layer on the back side of the decorative layer). By forming the synthetic resin backer layer, excellent caster resistance can be imparted to the decorative sheet.

  The resin component constituting the synthetic resin backer layer is not limited, but a thermoplastic resin such as polyethylene (PE) (including low density polyethylene, linear low density polyethylene, medium density polyethylene, and high density polyethylene), Olefin resins such as polypropylene (PP) (including homopolypropylene), ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene; polyvinyl alcohol; polyethylene terephthalate (PET); Amorphous polyethylene terephthalate (A-PET); highly heat-resistant polyalkylene terephthalate [for example, polyethylene terephthalate in which a part of ethylene glycol is substituted with 1,4-cyclohexanedimethanol, diethylene glycol or the like, the so-called trade name PET-G ( Manufactured by Eastman Chemical Company); Polybutylene terephthalate (PBT); Polycarbonate; Polyarylate; Polyethylene naphthalate; Polyethylene naphthalate-isophthalate copolymer; Polyimide; Polystyrene; Polyamide; ABS (Acrylonitrile-butadiene-styrene copolymer) ) And the like. These resins can be used alone or in combination of two or more. Of the resin components constituting the synthetic resin backer layer, an olefin resin is preferable.

  The synthetic resin backer layer further contains hollow beads. Since the hollow beads have a low thermal conductivity by having a void layer, excellent thermal insulation can be imparted to the decorative sheet by containing the hollow beads in the synthetic resin backer layer. The hollow beads mean beads having cavities therein, and are clearly distinguished from solid beads filled with contents.

  The average particle diameter of the hollow beads can be measured by a known method such as a laser diffraction method, a Coulter counter method, or a precipitation method. The average particle diameter means a particle diameter (D50) corresponding to a cumulative frequency of 50%.

  Content of a hollow bead is 10-40 mass parts with respect to 100 mass parts of resin components which comprise a synthetic resin backer layer. When the content of the hollow beads is within the above range, excellent heat insulating properties, scratch resistance, and the like can be imparted to the decorative sheet. When the content of the hollow beads is less than 10 parts by mass, the heat insulating property may be inferior, and when it exceeds 40 parts by mass, the scratch resistance may be inferior. A preferable content of the hollow beads is 20 to 40 parts by mass with respect to 100 parts by mass of the resin component forming the surface protective layer.

  The components of the hollow beads include acrylic resin, urethane resin (polyurethane), polyethylene resin, polypropylene resin, polycarbonate resin, polyvinyl chloride resin, melamine resin, nylon resin (polyamide resin), polystyrene resin, styrene-acrylic copolymer resin. Polyester resin, polybutadiene resin, polyisobutylene resin, polyacrylamide resin, polyvinyl alcohol resin, polyvinylidene chloride resin, polymaleic anhydride resin, polyvinylidene fluoride resin, polyacrylonitrile resin, polyvinyl acetate resin, polyethylene terephthalate resin, etc. Organic hollow beads (resin hollow beads) formed from resin or each copolymer resin; silicic acid (silicic acid) soda glass, aluminosilicate glass, borosilicate soda glass, soda lime Hollow glass beads, etc. rightist acid glass; Shirasu and natural volcanic glass-based, such as obsidian hollow beads and raw material; hollow beads (inorganic hollow beads) which are formed from inorganic compounds such as and the like. The organic hollow beads are familiar with the resin component constituting the synthetic resin backer layer. Since the inorganic hollow beads are hard, the shape is maintained without being crushed. Among the hollow beads, inorganic hollow beads are preferable.

  The surface of the inorganic hollow beads may be surface-treated with a coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane. In this case, by using according to the kind of binder resin, while being able to improve the filling rate to the binder resin of a hollow bead, affinity with binder resin can be improved. As a result, an effect that the strength of the synthetic resin backer layer is improved is obtained. In the present specification, the hollow beads may be partially omitted by adding a resin name before the name of the beads. For example, hollow beads made of acrylic resin can be called acrylic beads. The hollow beads can be used alone or in combination of two or more.

  Examples of the method for forming the synthetic resin backer layer include calender molding, extrusion molding of molten resin, and the like. Among these, extrusion molding of a molten resin is preferable, and for example, extrusion molding using a T die is more preferable.

  As a method of bonding the back surface of the base sheet and the synthetic resin backer layer, a method of bonding the base sheet and the synthetic resin backer layer obtained by extruding the molten resin by heat fusion, the base sheet and Examples include a method of bonding by providing an adhesive layer B (and a primer layer as necessary) between the synthetic resin backer layer and the like.

  As a method for adhering the back surface of the synthetic resin backer layer and the foamed resin backer layer described later, an adhesive layer C (and a primer layer as necessary) is provided between the synthetic resin backer layer and the foamed resin backer layer. And a method of co-extrusion with a multilayer extruder using a synthetic resin backer layer and a foamed resin backer layer or a foaming agent-containing resin layer for forming a foamed resin backer layer.

  As a method of co-extrusion molding with a multilayer extruder, it can be produced by molding into a sheet (film) by an inflation method (round die extrusion method), a T-die extrusion method or the like. In the case of coextrusion film formation, a resin layer composed of two or more of the synthetic resin backer layer and the foamed resin layer backer layer or the foaming agent-containing resin layer can be easily formed. For extrusion film formation, for example, a multi-manifold type or a feed block type T-die may be used.

  The adhesive layer B and / or C can be obtained by applying and drying the same adhesive as the adhesive layer A. Also about the thickness after drying of the adhesive bond layer B and / or C, about 0.1-30 micrometers is preferable similarly to the said adhesive bond layer A, and about 1-20 micrometers is more preferable.

  The synthetic resin backer layer may be colored as necessary. For example, when the backer layer is colored in the same color as the wood board, only the side surface of the backer layer is not conspicuous when used as a decorative material, and excellent design properties can be exhibited. Moreover, the effect which relieves the influence of the cloudiness based on the foaming resin backer layer mentioned later is also acquired. It does not limit as a coloring agent which can be used at the time of coloring, The coloring agent etc. which can be used for a base material sheet can be used.

  The thickness (thickness) of the synthetic resin backer layer is 200 to 600 μm. When the thickness of the synthetic resin backer layer is within the above range, excellent flaw resistance can be imparted to the decorative sheet, and the problem of cohesive failure of the foamed resin backer layer due to the temperature difference is also solved. If the thickness of the synthetic resin backer layer is less than 200 μm, the scratch resistance may be inferior. If the thickness exceeds 600 μm, the problem of cohesive failure of the foamed resin backer layer due to the temperature difference may not be solved. A preferable thickness of the synthetic resin backer layer is 200 to 450 μm.

  The synthetic resin backer layer may be subjected to known easy adhesion treatment such as corona discharge treatment, plasma treatment, degreasing treatment, surface roughening treatment, and the like, if necessary.

Foamed resin backer layer In the present invention, a foamed resin backer layer (foamed resin layer) is provided on the back side of the synthetic resin backer layer. By forming the foamed resin backer layer, even when a decorative material is obtained by laminating an adherend such as a wooden base material, the problem of unevenness due to the adherend is solved. Hateful). Specifically, the decorative sheet of the present invention has the effect of the adherend (the effect of (i) the unevenness existing on the surface of the adherend, (ii) the unevenness of polishing, the knots of wood, etc. (so-called duck). Impact, etc.) can be mitigated.

  As a method for forming the foamed resin backer layer, a conventionally known resin foaming technique can be employed. For example, (1) a method in which a thermoplastic resin pellet or bead is impregnated with gas, heated and melted by an extruder, and foamed when exiting the die, and (2) a thermoplastic resin pellet or bead is extruded by an extruder. A method of heating and melting, injecting and kneading gas into the mold, and foaming when the die exits, (3) Pellet or beads of thermoplastic resin containing foaming agent is heated and melted with an extruder, and the die A sheet having an unfoamed foaming agent-containing resin layer is obtained at the time of exiting, and a foaming agent-containing resin layer is crosslinked and foamed by electron beam irradiation or heating in post-processing, (4) thermoplastic resin pellets And a chemical foaming agent that decomposes at the molding temperature to generate gas, and is heated and melted with an extruder, and foamed when exiting the die. A commercially available foam sheet may be used for the foamed resin backer layer.

  Examples of the foaming agent include thermally decomposable foaming agents such as azodicarbonamide, azobisisobutyronitrile, N—N′-dinitrosopentamethylenetetramine, oxybisbenzenesulfonylhydrazide, sodium hydrogen carbonate, and potassium hydrogen carbonate; Examples thereof include a microcapsule type foaming agent in which a thermally expanded gas such as hexane or isobutane is enclosed in a resin spherical shell such as acrylonitrile. The addition amount is preferably about 1 to 10 parts by mass with respect to 100 parts by mass of the resin component of the foam, and the expansion ratio is 5 to 15 times.

  Examples of the thermoplastic resin include polyethylene (including low density polyethylene, linear low density polyethylene, medium density polyethylene, and high density polyethylene), polypropylene (including homopolypropylene), ethylene-α-olefin copolymer, poly Methylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer (EVA), saponified ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and these Olefin resins such as acid-modified products and ionomer resins; Polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, polycarbonate, polyarylate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer; Amide resins; polyimide resin; polystyrene resins; polyacrylic resins, polyvinyl alcohol resins; ABS resins. Of the thermoplastic resins, olefin resins are preferred. The thermoplastic resin is more preferably resin-crosslinked. As said resin bridge | crosslinking, the said irradiation is mentioned, for example. The resin crosslinking of the thermoplastic resin may be before foaming or after foaming of the foaming agent-containing resin layer, but is preferably before foaming.

  The cell structure of the foamed resin backer layer may be either a closed cell structure (cell structure) or an open cell structure (sponge structure), but is preferably a closed cell structure. Since the cell structure of the foamed resin backer layer is a closed cell structure, (1) there is no heat transfer due to the flow of gas between the cells, and (2) it contains a sheet-like foaming agent before the foamed resin backer layer is formed. Even if the opening formed by punching out or cutting out the resin layer (heat insulating sheet) is sealed with a decorative layer to form a plurality of hollow spaces, the large closed cells (spaces) in which the hollow spaces are independent from each other It becomes. Therefore, the foamed resin backer layer having a closed cell structure is more excellent in heat insulation. In addition, when the inner and outer heat insulating sheets and the inner and outer heat insulating members are cut into a desired shape and size, the heat insulating property generated by moisture being transferred from the end surface of the sheet or member to the inside of the foamed resin backer layer or the hollow space. In addition, a decrease in moisture resistance can be prevented by employing the closed cell structure.

  The thickness of the foamed resin backer layer is 200 to 1000 μm. When the thickness of the foamed resin backer layer is within the above range, the decorative sheet can be provided with excellent heat insulation, scratch resistance and caster resistance, and the problem of unevenness caused by the adherend is eliminated. Is done. When the thickness of the foamed resin backer layer is less than 200 μm, the heat insulation is inferior and the problem of unevenness due to the adherend may not be solved. Further, when the thickness of the foamed resin backer layer exceeds 1000 μm, the scratch resistance and caster resistance may be inferior. A preferable thickness of the foamed resin backer layer is 500 to 1000 μm.

The foamed resin backer layer has an apparent density of 100 to 400 kg / m ³ . When the apparent density of the foamed resin backer layer is within the above range, it is possible to impart excellent caster resistance to the decorative sheet and solve the problem of unevenness due to the adherend. When the apparent density of the foamed resin backer layer is less than 100 kg / m ³ , caster resistance may be inferior. In addition, when the apparent density of the foamed resin backer layer exceeds 400 kg / m ³ , the problem of unevenness due to the adherend may not be solved. The apparent density of the preferred foamed resin backer layer is 100 to 350 kg / m ³ . In the present specification, the apparent density of the foamed resin backer layer is measured according to JIS K 7222.

  A primer layer may be provided on the back surface of the foamed resin backer layer. For example, it is advantageous when a foamed resin backer layer and an adherend are bonded to produce a decorative material. The contents of the primer layer, such as components, formation method, and thickness, are the same as those of the back primer layer described above.

≪Cosmetic materials≫
A decorative material can be obtained by bonding and bonding an adherend to the back surface of the decorative sheet of the present invention.

The material of various adherends is not particularly limited, and examples thereof include inorganic non-metallic materials, metallic materials, woody materials, and plastic materials.
Specifically, in inorganic non-metallic systems, for example, papermaking cement, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), pulp cement, wood chip cement, asbestos cement, calcium oxalate, Non-ceramic ceramic materials such as gypsum and gypsum slag, ceramic materials such as earthenware, ceramics, porcelain, setware, glass, and glazing.
In a metal system, metal materials (metal steel plate), such as iron, aluminum, and copper, are mentioned, for example.
In the wood system, for example, wood base materials such as veneer, wood plywood, particle board, fiber board, laminated wood made of cedar, straw, firewood, lawan, teak and the like can be mentioned. Examples of wood plywood include softwood plywood and afforestation wood plywood, which are known as lauan substitute plywood. Specifically, examples of the conifer include pine pine and karamatsu. Examples of afforestation trees include poplar, falkata, acacia, chamelele, eucalyptus, terminaria and the like.
In the plastic system, for example, resin materials such as polypropylene, ABS resin, and phenol resin can be used.

  When a wood plywood is used as the adherend, the thickness is not limited, but is preferably about 3 to 15 mm, and more preferably about 10 to 15 mm. Further, the number of laminated wood single plates constituting the wood plywood (number of plies) is not limited, but usually 3 to 7 sheets are preferable, and 5 to 7 sheets are more preferable.

  Even when the decorative sheet of the present invention is obtained by laminating adherends such as a wooden base material, the problem of unevenness due to the adherend is solved. Therefore, even when a softwood plywood having many nodes or an afforestation tree plywood with remarkable unevenness (swells) is used as the adherend, the above-described excellent effect is exhibited, which is advantageous.

  The shape of such an adherend is not particularly limited, and may be a flat plate in consideration of installation on a flooring or the like.

  In order to bond the adherend and the decorative sheet, for example, an adhesive can be used. Examples of the adhesive include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, butadiene / acrylonitrile rubber, neoprene rubber, natural rubber, and the like as active ingredients. Any known adhesive can be used.

  After bonding the adherend and the decorative sheet, for example, according to the characteristics of the final product, cutting, use of a tenoner, sag processing, provision of a V-shaped groove, chamfering on four sides, and the like may be performed.

  The decorative sheet of the present invention can be used for various uses such as floors, joinery, stairs and walls. In addition, the decorative material of the present invention can be used for various applications such as a decorative material for floors, a decorative material for joinery, a decorative material for stairs, and a decorative material for walls.

  In the decorative sheet of the present invention, two different layers having specific physical properties (that is, a synthetic resin backer layer and a foamed resin backer layer) are sequentially laminated on the back side of the decorative layer, and the synthetic resin backer layer is formed of hollow beads. Is contained in a specific amount. Therefore, the decorative sheet of the present invention has solved the problem of unevenness due to the adherend even when a decorative material is obtained by laminating the adherend such as a wooden substrate, and the temperature difference The problem of cohesive failure of the resulting foamed resin backer layer is also solved. Furthermore, it is excellent in heat insulation, scratch resistance and caster resistance.

Drawing 1 is a mimetic diagram showing an example (layer composition conceptual diagram) of an embodiment of a decorative sheet of the present invention.

  The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Example 1
An acrylic urethane resin primer layer (back primer layer, thickness 2 μm) was provided on the back surface of a base sheet made of colored polypropylene having a thickness of 60 μm. Next, an acrylic resin-containing ink was used on the front surface of the base sheet, and a 2 μm pattern layer was formed by gravure printing. A polyester resin adhesive layer (thickness 3 μm) was formed on the pattern layer.

  Next, on the adhesive layer, a transparent polypropylene resin was laminated by extrusion lamination to form a transparent resin layer (thickness 80 μm). After the corona discharge treatment was performed on the front surface of the transparent resin layer, a primer layer (thickness: 2 μm) was formed by applying a two-component curable urethane resin on the transparent resin layer.

  Next, bifunctional urethane acrylate oligomer (weight average molecular weight: 1500, glass transition temperature (Tg): −55 ° C.) 80 parts by mass on the primer layer, and hexafunctional aliphatic urethane acrylate oligomer (weight average molecular weight: 1500) Glass transition temperature (Tg): 200 ° C or higher, “UA306H (trade name)” manufactured by Kyoeisha Chemical Co., Ltd.) 20 parts by mass of ionizing radiation curable resin applied by roll coating method, oxygen concentration 200 ppm or less In this environment, an electron beam was irradiated using an electron beam irradiation device under the conditions of an acceleration voltage of 175 keV and 5 Mrad to form a surface protective layer (thickness 15 μm). Thereby, a decorative layer intermediate (sheet) was obtained.

A decorative layer (decorative sheet) with an embossed pattern formed by embossing (sheet temperature 120-160 ° C, pressure 10-40 kg / cm ² ) from the outermost layer side (surface protective layer side) of the decorative layer intermediate Intermediate) was obtained.

After applying urethane adhesive on the back of the base sheet of the decorative layer, 100 parts by mass of transparent polypropylene resin and glass (glass) hollow beads (average particle size 35 μm, true specific gravity 0.22 g / cm ³ , trade name: 10 parts by mass of Glass Bubbles S22 (manufactured by Sumitomo 3M Limited, soda lime borosilicate glass) was heated and melt extruded with a T-die extruder to form a synthetic resin backer layer (thickness 200 μm).

Next, after forming a polyester resin adhesive layer on the back surface of the synthetic resin backer layer, a foamed polyethylene sheet (thickness 800 μm, apparent density 130 kg / m ³ , trade name: polyethylene foam “PE Lite” LSL-8, ) Technoform Japan) was laminated to form a foamed resin backer layer (thickness 800 μm) to obtain a decorative sheet.

  Further, a decorative material was prepared by pasting the decorative sheet on a softwood plywood (thickness 12 mm) via a vinyl acetate aqueous emulsion adhesive.

Examples 2-16 and Comparative Examples 1-17
The following (a) to (k):
(a) content of hollow beads,
(b) the thickness of the synthetic resin backer layer,
(c) the thickness of the foamed resin backer layer,
(d) apparent density of the foamed resin backer layer,
(e) a resin component constituting the synthetic resin backer layer,
(f) a resin component constituting the foamed resin backer layer,
(g) Types of hollow beads (components, average particle size, specific gravity, etc.)
(h) the thickness of the decorative layer,
(i) whether or not a synthetic resin backer layer is formed,
(j) presence or absence of formation of a foamed resin backer layer,
(k) positional relationship between the synthetic resin backer layer and the foamed resin backer layer,
(l) Cosmetic sheets and cosmetic materials of Examples 2 to 16 and Comparative Examples 1 to 17 were produced in the same manner as in Example 1 except that the layer containing the hollow beads was appropriately changed. The above (a) to (k) are as shown in Table 1 below.

In addition, the change of said (g)-(k) is demonstrated below.
Example 13 differs from Example 1 in (g) the type of hollow beads. Example 13 uses hollow polyacrylonitrile resin beads (average particle size 80 μm, true specific gravity 0.02 g / cm ³ , trade name: Matsumoto Microsphere F-80ED, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) as hollow beads. Yes.
-Example 16 is different from Example 1 in terms of the thickness of the decorative layer of (h). In Example 16, the thickness of the base material sheet made of colored polypropylene is 140 μm, and the thickness of the entire decorative layer is 244 μm.
Comparative Examples 13 to 15 and 17 differ from Example 1 in terms of (i) the presence or absence of formation of a synthetic resin backer layer. In Comparative Examples 13 to 15 and 17, the polyester resin adhesive is applied to the back surface of the decorative layer, and then the synthetic resin backer layer is not formed, but the foamed resin backer layer is directly bonded.
Comparative Examples 11 and 12 differ from Example 1 in terms of (j) presence / absence of formation of a foamed resin backer layer. In Comparative Examples 11 and 12, a decorative sheet was obtained without forming the adhesive layer and the foamed resin backer layer on the back surface of the synthetic resin backer layer.
Comparative Example 16 is different from Example 1 in terms of the positional relationship between the synthetic resin backer layer and the foamed resin backer layer. In Comparative Example 16, a polyester resin adhesive was applied to the back surface of the decorative layer, and then a foamed resin backer layer was bonded to the back surface of the foamed resin backer layer without forming a synthetic resin backer layer. After the resin adhesive layer is applied, a synthetic resin backer layer is formed.
Comparative Example 17 differs from Example 1 not only in (i) the presence or absence of the formation of a synthetic resin backer layer, but also in the point of (l) a layer containing hollow beads. In Comparative Example 17, the hollow beads used in Example 1 are contained in the foamed resin backer layer. The content of hollow beads (glass hollow beads) is 30 parts by mass with respect to 100 parts by mass of the resin component constituting the foamed resin backer layer.
Others are as shown in Table 1 below.

≪Evaluation test for decorative sheet or cosmetic material≫
Evaluation test 1: Insulation test (evaluation test to determine whether it is difficult to feel cold)
The following evaluation tests were performed on the decorative materials produced in Examples 1 to 16 and Comparative Examples 1 to 17. Specifically, for 15 adult men and women in their 20s and 40s, (1) wearing socks, (2) wearing stockings, and / or (3) bare feet, the above cosmetics are usually walked and walked. It was. Moreover, the same walk was made also about the general-purpose wood floor (the general veneer painting floor currently marketed).
(Evaluation method)
◎: More than 10 adult men and women did not feel cold compared to general-purpose wood floor ○: More than 8 adult men and women did not feel cold compared to general-purpose wood floor △: More than 6 adult men and women , Did not feel cold compared to the general-purpose wood floor ×: △, ○ or ◎ that there are 5 or less adult men and women who did not feel cold compared to the general-purpose wood floor is a product.

Evaluation test 2: Scratch resistance test (Hoffman scratch test)
The cosmetic materials produced in Examples 1 to 16 and Comparative Examples 1 to 17 were evaluated by scratching the surface of the cosmetic material with a load of 1000 g using a Hoffman scratch tester (BYK-GARDNER).
(Evaluation method)
○: Almost no change on the surface of the decorative material Δ: Slight whitening scratches are observed on the surface of the decorative material ×: Δ or ○ where whitening scratches are conspicuous on the surface of the decorative material is acceptable as a product.

Evaluation test 3: Castor resistance test (caster resistance test)
The cosmetic materials produced in Examples 1 to 16 and Comparative Examples 1 to 17 were tested and evaluated using a caster resistant device L6-04 (manufactured by Asano Machinery Co., Ltd.). Specifically, after moving the caster on the cosmetic material, 15 adults in their 20s and 40s were evaluated for the state of the recesses attached to the cosmetic material by visual observation.

In the caster-resistant test apparatus, the cosmetic material to be tested was fixed to the sample fixing base. The caster fixing base was raised by the adjustment handle so that the three casters did not contact the surface of the decorative material, and then the weight was placed on the load base so that the weight would be 70 kg. The rotation speed was set at 20 rpm, half rotation every 5 minutes, 1000 rotations, and the adjustment handle was turned to lower the caster fixing base on the surface of the decorative material. The test was started by turning on the start switch of the rotary drive device of the caster fixed base. After the test, the adjustment handle was turned to float the caster fixing base, and the cosmetic material was taken out for evaluation.
(Evaluation method)
◎: More than 10 adult men and women feel that the recesses on the cosmetic material are inconspicuous ○: More than 8 adult men and women feel that the recesses on the makeup material are inconspicuous △: More than 6 adult men and women make up It is felt that the concave portion attached to the material is inconspicuous. ×: Δ, ○, or ◎, in which there are 5 or less adult men and women who feel that the concave portion attached to the cosmetic material is inconspicuous, is a product.

Evaluation test 4: Appearance evaluation test (evaluation test of whether or not the unevenness of the adherend is conspicuous)
It evaluated whether the unevenness | corrugation of the wooden base material which is a to-be-adhered material was conspicuous with respect to the decorative material produced in Examples 1-16 and Comparative Examples 1-17. Specifically, whether or not the unevenness on the surface of the wooden base material appears to appear on the surface of the decorative material (the surface of the decorative sheet) when a decorative sheet is laminated on the wooden base material. evaluated. In this evaluation test, as described above, a decorative sheet is laminated on a wooden base material to obtain a cosmetic material, and then the surface of the cosmetic material is observed while applying light from a fluorescent lamp so as to be oblique to the cosmetic material. Was done.
(Evaluation method)
◎: More than 10 adult men and women feel that the unevenness of the wooden substrate is inconspicuous ○: More than 8 adult men and women feel that the unevenness of the wooden substrate is inconspicuous △: More than 6 adult men and women are wooden I feel that the unevenness of the base material is inconspicuous. X: Δ, ○, or ◎ that there are 5 or less adult men and women who feel that the unevenness of the wooden base material is inconspicuous is passed as a product.

Evaluation test 5: Cohesive failure evaluation test (evaluation of in-layer peeling of foamed resin backer layer)
For the decorative materials produced in Examples 1 to 16 and Comparative Examples 1 to 17, the cohesive failure of the foamed resin backer layer was evaluated. Specifically, in accordance with the “JAS Plywood Cold Heat Repeat A Test”, one cycle was the cold heat repeat test (“Leave cosmetic material at 80 ° C. for 2 hours → Leave cosmetic material at −20 ° C. for 2 hours”) Occasionally, a 10-cycle test was performed and then evaluated by visual observation.
(Evaluation method)
○: There is no in-layer peeling in the foamed resin backer layer. Δ: There is some in-layer peeling in the foamed resin backer layer, but it is inconspicuous. ×: There is in-layer peeling in the foamed resin backer layer. As pass.

Physical property measurement 1: Apparent density measurement The apparent density of the foamed resin backer layer was measured according to JIS K 7222.

  The results are shown in Table 1 below.

1.Back primer layer
2. Foamed resin backer layer
3.Synthetic resin backer layer
4.Base sheet
5. Pattern pattern layer
6. Adhesive layer
7.Transparent resin layer
8. Surface protective layer
9. Makeup layer
10. Hollow beads

Claims (6)

A decorative sheet in which a synthetic resin backer layer and a foamed resin backer layer are sequentially laminated on the back side of the decorative layer,
(1) The synthetic resin backer layer contains hollow beads,
(2) The content of the hollow beads is 10 to 40 parts by mass with respect to 100 parts by mass of the resin component constituting the synthetic resin backer layer,
(3) The synthetic resin backer layer has a thickness of 200 to 600 μm,
(4) The foamed resin backer layer has a thickness of 200 to 1000 μm,
(5) A decorative sheet, wherein the foamed resin backer layer has an apparent density of 100 to 400 kg / m ³ .   The decorative sheet according to claim 1, wherein the cell structure of the foamed resin backer layer is a closed cell structure.   The decorative sheet according to claim 1 or 2, wherein the synthetic resin backer layer is laminated on the foamed resin backer layer via an adhesive.   The makeup according to claim 1 or 2, wherein the synthetic resin backer layer and the foamed resin backer layer or the foaming agent-containing resin layer for forming the foamed resin backer layer are coextruded by a multilayer extruder. Sheet.   The decorative sheet according to claim 1, wherein the decorative layer is a decorative intermediate sheet, decorative paper, melamine plate, or veneer in which one or two or more resin layers are laminated on a base sheet.   A decorative material obtained by laminating the decorative sheet according to any one of claims 1 to 5 on an adherend.

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