JP6115247B2 - Cosmetic sheet and cosmetic material using the same - Google Patents

Description

  The present invention relates to a decorative sheet and a decorative material using the decorative sheet. Specifically, the present invention relates to a decorative sheet using a polyolefin resin, which has good adhesion to the polyolefin resin layer and can be produced by a simple method, and a decorative material using the decorative sheet.

  Conventionally, an olefin-based decorative sheet using a polyolefin resin is generally used as a surface material of an interior material because of its high designability and functionality. As a layer configuration, for example, a mode in which a pattern layer, an adhesive layer, a polyolefin transparent resin layer, and a surface protective layer are sequentially laminated on a base sheet is well known.

  Since the polyolefin resin is nonpolar, the olefin-based decorative sheet is generally difficult to ensure adhesiveness. As the adhesive layer, a polyurethane-based adhesive composed of a polyester polyol and an isocyanate compound is often used. However, in the case of the layer configuration exemplified above, the adhesiveness between the pattern layer and the polyolefin transparent resin layer is high. You may not get enough.

  Then, after forming a pattern layer on a base material sheet, the adhesiveness is improved by corona treatment or ozone treatment of the surface. As another method, the adhesiveness is improved by using a part of the polyolefin transparent resin layer that is in contact with the adhesive layer as an easily adhesive resin layer. For example, in FIG. 1, a decorative sheet in which the adhesiveness of the transparent resin layer is improved by providing the easy-adhesion resin layer 6 between the transparent resin layer 7 and the adhesive layer 5 is laminated on the adherend 1. A decorative material is shown.

  As an example using an easily adhesive resin layer, for example, Patent Document 1 is known. Specifically, Patent Document 1 discloses a decorative sheet in which a decorative sheet, an adhesive layer, and two or more polyolefin resin layers are sequentially laminated on a base sheet, and the polyolefin resin in contact with the adhesive layer It is disclosed that the layer is an easily adhesive resin layer made of a specific resin composition (claims 1 to 3, paragraphs [0010] to [0028] in Patent Document 1). As the easy-adhesion resin for the easy-adhesion resin layer, generally, those obtained by acid-modifying polyolefin resins to impart polarity are well known.

  However, when a part of the polyolefin transparent resin layer that is in contact with the adhesive layer is an easily adhesive resin layer, there are the following problems. That is, the easy-adhesion resin layer has good initial adhesiveness, but has insufficient heat resistance and water resistance, and thus the interlaminar adhesion tends to decrease with time. Further, the easily adhesive resin layer tends to be whitened during bending. Furthermore, the easily adhesive resin layer tends to be expensive to manufacture.

  In addition, the easy-adhesive resin layer is often used in contact with an adhesive layer made of a polyurethane-based adhesive or the like, but it takes time until the adhesive layer is cured. After winding, it is necessary to cure at a predetermined temperature until the adhesive layer is cured, which is a factor that takes time to produce a decorative sheet.

  Therefore, without using an adhesive layer or an easy-adhesion resin layer, the polyolefin resin layer has good adhesion, and has whitening resistance during bending and can be produced by a simple method. Development of a decorative decorative sheet is desired.

JP 2008-272957 A

  The present invention ensures good adhesion of the polyolefin resin layer without using an adhesive layer or an easily adhesive resin layer, and has whitening resistance during bending and can be produced by a simple method. An object is to provide an olefin-based decorative sheet. Another object of the present invention is to provide a cosmetic material using the olefin-based decorative sheet.

  As a result of extensive research, the present inventors have found that the above object can be achieved when a specific heat seal layer is used instead of using an adhesive layer or an easily adhesive resin layer, and the present invention has been completed. It came to do.

That is, the present invention relates to the following decorative sheet and a decorative material using the same.
1. On the base sheet, a decorative sheet having a pattern layer, a heat seal layer and a transparent resin layer containing a polyolefin resin in that order,
The heat seal layer, Ri hardened layer der of the coating film formed from an aqueous emulsion comprising a modified polyolefin resin as a dispersoid,
The modified polyolefin resin has a hydrophilic polymer bound thereto,
A decorative sheet characterized by that.
2. The modified polyolefin resin is made of polyolefin resin, styrene, methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, dichlorostyrene, divinylbenzene, diallylbenzene, divinylnaphthalene, diallylisophthalate, 1,6-hexanediol diacrylate, Selected from the group consisting of methylolpropane triacrylate, pentaerythritol triacrylate, ethylene glycol dimethacrylate, (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, anhydrides of these acids, and monoesters of the acid anhydrides Item 2. The decorative sheet according to Item 1, wherein at least one selected from the group has a graft polymerized structure.
3. The modified polyolefin resin is a maleic anhydride-modified propylene polymer or a chlorinated product thereof, a maleic anhydride-modified ethylene-propylene copolymer or a chlorinated product thereof, a maleic anhydride-modified propylene-butene copolymer or a chloride thereof, or a maleic anhydride. Acid-modified ethylene-propylene-butene copolymer or its chloride, acrylic acid-modified propylene polymer or its chlorinated product, acrylic acid-modified ethylene-propylene copolymer or its chlorinated product, and acrylic acid-modified propylene-butene copolymer Ri least 1 Tanedea selected from coalescence or the group consisting of the chlorides, the hydrophilic polymer is attached, the decorative sheet according to item 1.
4). Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the pattern layer and the transparent resin layer are in direct contact with the heat seal layer.
5. Any of the above items 1 to 4, wherein the hydrophilic polymer is at least one selected from the group consisting of poly (meth) acrylic resins, polyether resins, polyvinyl alcohol resins, starch, corn starch, gelatin, and celluloses. decorative sheet according to any.
6). Item 6. The decorative sheet according to any one of Items 1 to 5, wherein the pattern layer includes a thermosetting resin.
7). Item 7. The decorative sheet according to any one of Items 1 to 6, which has an embossed pattern on the front surface.
8). Item 8. The decorative sheet according to any one of Items 1 to 7, having a synthetic resin backer layer on the back surface of the base sheet.
9. A decorative sheet, wherein the decorative sheet according to any one of Items 1 to 8 is laminated on an adherend through an adhesive layer.
10. On the base sheet, a method for producing a decorative sheet having a pattern layer, a heat seal layer, and a transparent resin layer containing a polyolefin resin in the order,
(1) The process of forming a pattern layer on a base material sheet,
(2) A step of forming a heat seal layer by applying an aqueous emulsion containing a modified polyolefin resin to which a hydrophilic polymer is bonded as a dispersoid in a mode of covering the pattern layer.
(3) A step of heat-sealing the transparent resin layer by thermally laminating a transparent resin layer containing a polyolefin resin on the heat-seal layer,
The manufacturing method characterized by including.
11. The manufacturing method according to Item 10, wherein the thermal lamination is thermal lamination by heat brought in when the transparent resin layer is melt-extruded and formed on the heat seal layer.
12 Item 12. The method according to Item 10 or 11, further comprising a step of embossing the front surface.
13. The manufacturing method according to any one of Items 10 to 12, wherein the pattern layer and the transparent resin layer are in direct contact with the heat seal layer, respectively.

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

The decorative sheet of the present invention has a pattern resin layer, a heat seal layer and a transparent resin layer containing a polyolefin resin in that order on a base sheet, and the heat seal layer contains a modified polyolefin resin as a dispersoid. It is the hardened layer of the coating film formed from the aqueous emulsion containing as characterized by the above-mentioned.

  The decorative sheet of the present invention having the above features employs a specific heat seal layer in place of the conventional adhesive layer and easy-adhesion resin layer, and the heat seal layer comprises an aqueous emulsion containing a modified polyolefin resin as a dispersoid. By being a cured layer of the formed coating film, good adhesiveness of the transparent resin layer containing the polyolefin resin is ensured. In addition, the heat seal layer has whitening resistance at the time of bending unlike the conventional easy-adhesion resin layer. Furthermore, since the decorative sheet of the present invention adheres the transparent resin layer by heat sealing, the curing process required when using the conventional adhesive layer is unnecessary and can be easily produced.

The layer structure of the decorative sheet of the present invention is not particularly limited as long as it has a pattern resin layer, a heat seal layer, and a transparent resin layer containing a polyolefin resin in that order on the base sheet. For example, as a suitable layer configuration, a layer configuration having a pattern layer, a heat seal layer, a transparent resin layer containing a polyolefin resin, and a transparent surface protective layer in that order on the base sheet is preferable. Hereinafter, each layer will be described by taking this preferable layer configuration as an example. In the decorative sheet of the present invention, the transparent resin layer (the transparent surface protective layer in the case of having a transparent surface protective layer) is a so-called “front surface” (surface visually recognized after construction). Therefore, in this specification, the direction in which the transparent resin layer is present when viewed from the base sheet is referred to as “front” or “up”, and the opposite direction is referred to as “back” or “down”.
(Substrate sheet)
Although it does not limit as a base material sheet, the base material sheet which contains polyolefin resin as a resin component is preferable. In practice, a sheet made of polyolefin resin is used.

  It does not specifically limit as polyolefin resin, The thing normally used in the field | area of the decorative sheet can be used. For example, polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-propylene-butene copolymer, polyolefin-based thermoplastic elastomer, etc. Is mentioned. Of these, polypropylene, polyolefin thermoplastic elastomer, and the like are particularly preferable.

  A homopolymer or copolymer mainly composed of polypropylene is also preferable, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and an α having 2 to 20 carbon atoms other than propylene and having a polypropylene crystal part. -Olefins. In addition, a propylene-α-olefin copolymer containing 15 mol% or more of a comonomer of ethylene, butene-1,4-methylpentene-1, hexene-1, or octene-1 is also preferable.

  The polyolefin thermoplastic elastomer is preferably a mixture of isotactic polypropylene in the hard segment and atactic polypropylene in the soft segment in a weight ratio of 80:20.

  The polyolefin resin may be formed into a film by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like.

  The thickness of the substrate sheet is not particularly limited and can be set according to product characteristics, but is usually 50 to 250 μm, preferably about 50 to 100 μm.

  An additive may be mix | blended with a base material sheet as needed. Examples of the additive include a filler such as calcium carbonate and clay, a flame retardant such as magnesium hydroxide, an antioxidant, a lubricant, a foaming agent, and a colorant (see below). The blending amount of the additive can be appropriately set according to the product characteristics.

  It does not specifically limit as a coloring agent, Well-known coloring agents, such as a pigment and dye, can be used. For example, titanium white, zinc white, petal, vermilion, ultramarine blue, cobalt blue, titanium yellow, yellow lead, carbon black and other inorganic pigments; isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indanthrene Organic pigments (including dyes) such as blue RS and aniline black; metal pigments such as aluminum and brass; pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate. The coloring mode of the base sheet includes transparent coloring and opaque coloring (hiding coloring), and these can be arbitrarily selected. For example, when the ground color of the wooden board is concealed, opaque coloring may be selected. On the other hand, in order to make the ground pattern of the wooden board visible, transparent coloring may be selected.

  One or both surfaces of the base sheet may be subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, etc., as necessary. For example, when performing corona discharge treatment, the surface tension of the substrate sheet surface may be 30 dyne or more, preferably 40 dyne or more. The surface treatment may be performed according to a conventional method for each treatment.

  On one or both sides of the base sheet, a primer layer (for example, a backside primer layer for facilitating adhesion of a synthetic resin backer layer or an adherend, or a pattern layer is facilitated as necessary. A primer layer) may be provided.

  A primer layer can be formed by apply | coating a well-known primer agent to the single side | surface or both surfaces of a base material sheet. Examples of the primer agent include a urethane resin primer agent made of acrylic modified urethane resin, a primer agent made of urethane-cellulose resin (for example, a resin made by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton), and the like. Is mentioned.

Although the thickness of a primer layer is not specifically limited, Usually, 0.1-10 micrometers, Preferably it is about 1-5 micrometers.
(Pattern pattern layer)
A pattern layer is formed on the base sheet.

  The design pattern layer imparts design properties with a desired design to the decorative sheet, and the type of design is not particularly limited. Examples thereof include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern.

  The method for forming the pattern layer is not particularly limited. For example, a colored ink or coating obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin. What is necessary is just to form by the printing method etc. which used the agent.

  Examples of colorants include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments. Organic pigments such as aluminum powder, metal powder pigments such as bronze powder, pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; These colorants can be used alone or in admixture of two or more. These colorants may further contain fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.

  Examples of the binder resin include acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum Resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin and the like. These resins can be used alone or in admixture of two or more.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, acetic acid-2-methoxyethyl, acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene, etc. Chlorinated organic solvents; inorganic solvents such as water. These solvents (or dispersion media) can be used alone or in admixture of two or more.

  Examples of the printing method used for forming the pattern layer include a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method. When forming a solid pattern pattern layer, for example, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating Various coating methods such as a coating method may be mentioned. In addition, the hand-drawn method, the ink-sink method, the photographic method, the transfer method, the laser beam drawing method, the electron beam drawing method, the metal partial evaporation method, the etching method, etc. may be used or combined with other forming methods. Good.

  The thickness of the pattern layer is not particularly limited and can be set as appropriate according to product characteristics. The layer thickness at the time of coating is about 1 to 15 μm, and the layer thickness after drying is about 0.1 to 10 μm.

  On the pattern layer, a primer layer may be formed by applying a known primer agent. Examples of the primer agent include a urethane resin-based primer agent composed of an acrylic-modified urethane resin and the like, and a resin-based primer agent composed of a block copolymer of acrylic and urethane.

Although the thickness of a primer layer is not specifically limited, Usually, 0.1-10 micrometers, Preferably it is about 1-5 micrometers.
(Colored hiding layer)
A colored concealment layer may be further formed between the base sheet and the pattern layer as necessary. The colored masking layer is provided when it is desired to mask the ground color of the adherend from the front surface of the decorative sheet. Of course, when the base sheet is transparent, even when the base sheet is concealed, it may be formed to stabilize the concealment.

  As the ink for forming the colored masking layer, an ink for forming a pattern layer and capable of masking coloring can be used.

  The method for forming the colored concealment layer is preferably a method that can be formed so as to cover the entire base sheet (entirely solid). For example, the roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating method and the like described above are preferable.

The thickness of the colored concealing layer is not particularly limited and can be appropriately set according to product characteristics. The layer thickness at the time of coating is about 0.2 to 10 μm, and the layer thickness after drying is about 0.1 to 5 μm.
(Heat seal layer)
A heat seal layer is formed on the pattern layer.

  In the decorative sheet of the present invention, the heat seal layer is a cured layer of a coating film formed from an aqueous emulsion containing a modified polyolefin resin as a dispersoid.

  The modified polyolefin resin only needs to be modified so that the polyolefin resin can exist as a dispersoid in the aqueous dispersion medium. Here, as polyolefin resin, the same thing as what was illustrated by the item of the base material sheet can be used.

  In the present invention, the modified polyolefin resin is a styrene, methyl styrene, dimethyl styrene, ethyl styrene, isopropyl styrene, dichloro styrene, divinyl benzene, diallyl benzene, divinyl naphthalene, diallyl isophthalate, 1,6-hexanediol diester. Consists of acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethylene glycol dimethacrylate, (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, anhydrides of these acids, and monoesters of the acid anhydrides It is preferable that at least one modifying agent selected from the group is modified by binding. The mode of bonding is not limited, but from the viewpoint of dispersion stability in the modified polyolefin resin emulsion, it preferably has a graft polymerization structure.

  Each of the above modifiers has one or more ethylenically unsaturated groups, and the resulting modified polyolefin resin has good dispersibility in an aqueous dispersion medium and is easy to prepare an emulsion. Among the above modifiers, maleic anhydride and (meth) acrylic acid are particularly preferable. In addition, "(meth) acrylic acid" means acrylic acid or methacrylic acid, and the other description described as (meth) in this specification is the same.

  Among the above modified polyolefin resins, maleic anhydride modified propylene polymer or chlorinated product thereof, maleic anhydride modified ethylene-propylene copolymer or chlorinated product thereof, maleic anhydride modified propylene-butene copolymer or chloride thereof, Maleic anhydride-modified ethylene-propylene-butene copolymer or its chloride, acrylic acid-modified propylene polymer or its chlorinated product, acrylic acid-modified ethylene-propylene copolymer or its chlorinated product, and acrylic acid-modified propylene-butene It is preferably at least one selected from the group consisting of copolymers or chlorides thereof. Among these, maleic anhydride-modified propylene polymer, maleic anhydride-modified ethylene-propylene copolymer, and maleic anhydride-modified propylene-butene copolymer are particularly preferable.

  The amount of modification by the modifying agent is not limited, but the amount of modification is preferably in the range of 0.01 to 5 mmol / g, more preferably 0.03 to 1 mmol / g, relative to 1 g of the polyolefin resin before modification. .

  In the present invention, the modified polyolefin resin preferably further has a hydrophilic polymer bonded thereto. By binding the hydrophilic polymer, it becomes easy to prepare an aqueous emulsion in which the modified polyolefin resin is made finer. Thereby, the adhesiveness and water-resistant adhesiveness of the transparent resin layer in a decorative sheet can be improved more.

  The hydrophilic polymer is preferably at least one selected from the group consisting of poly (meth) acrylic resins, polyether resins, polyvinyl alcohol resins, starch, corn starch, gelatin and celluloses. Among these, it is preferable to use a poly (meth) acrylic resin, a polyether resin, or a polyvinyl alcohol resin from the viewpoint of easily adjusting the degree of hydrophilicity. The mode in which these hydrophilic polymers are bonded to the modified polyolefin resin is not limited, but graft polymerization and / or block polymerization are preferred, and graft polymerization is preferred from the viewpoint of dispersion stability in the emulsion.

  The binding amount of the hydrophilic polymer is not limited, but the binding amount is preferably in the range of 0.01 to 5 mmol / g, more preferably 0.05 to 1 mmol / g with respect to 1 g of the modified polyolefin resin. .

  The particle diameter of the modified polyolefin resin is preferably 3 μm or less, more preferably 1 μm or less, as a 50% particle diameter (50% particle diameter) cumulative from the smaller particle diameter in terms of volume, Most preferably, it is 0.5 μm or less. In addition, at a 90% particle size, it is preferably 1 μm or less, and more preferably 0.5 μm or less.

  By reducing the particle size of the modified polyolefin resin, the dispersion stability is improved, and the transparency is improved together with the adhesion and water-resistant adhesion. In the present invention, the particle diameter of the modified polyolefin resin in the aqueous emulsion is extremely small, and is a concept including a state where it is dispersed in a single molecule, that is, a state where it is substantially dissolved, adhesion, water-resistant adhesion and From the viewpoint of transparency, a dissolved state is preferable. Therefore, there is no particular limitation on the lower limit value of the particle diameter.

  The aqueous dispersion medium constituting the aqueous emulsion is not limited. For example, water; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, octane and decane; alicyclic rings such as cyclohexane and methylcyclohexane Formula aliphatic hydrocarbons; halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, chlorobenzene; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate; acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone Ketones such as cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, cyclohexanol, ethylene glycol, propylene glycol, and butanediol; Ethers such as dipropyl ether, dibutyl ether, and tetrahydrofuran; having two or more functional groups such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol, diacetone alcohol, etc. Organic solvents; polar solvents such as dimethylformamide and dimethyl sulfoxide are exemplified. These water and aqueous dispersion medium can be used alone or in admixture of two or more.

  The aqueous emulsion may contain known additives such as binder resins, colorants such as pigments and dyes, extender pigments, solvents, stabilizers, thickeners, plasticizers, catalysts, and crosslinking agents. Among these additives, as a crosslinking agent, a crosslinking agent having a self-crosslinking property, a compound having a plurality of functional groups that react with a carboxyl group in a molecule, a metal complex having a polyvalent coordination site, or the like is used. Can do. As the crosslinking agent, an isocyanate compound, a melamine compound, a urea compound, an epoxy compound, a carbodiimide compound, an oxazoline group-containing compound, a zirconium salt compound, a silane coupling agent, and the like are particularly preferable. These crosslinking agents can be used alone or in admixture of two or more.

  The content of the modified polyolefin resin in the aqueous emulsion is not limited, but is preferably 5 to 60% by mass, and more preferably 10 to 50% by mass.

  When forming a coating film of aqueous emulsion, for example, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating method, etc. are used. it can.

The thickness of the coating film of the aqueous emulsion is not particularly limited, and the layer thickness at the time of coating is about 1 to 15 μm, and the thickness of the heat seal layer after curing is about 0.1 to 10 μm.
(Transparent resin layer containing polyolefin resin)
A transparent resin layer containing a polyolefin resin is formed on the heat seal layer. The transparent resin layer includes any of colorless and transparent, colored and transparent, and translucent as long as it is transparent.

  As the polyolefin resin contained in the transparent resin layer, the same resin as exemplified in the item of the base sheet can be used, but polypropylene is most preferable. It is preferable that the transparent resin layer is substantially formed of a polypropylene resin.

  The transparent resin layer can be formed, for example, by forming a polyolefin resin by a calendering method, an inflation method, a T-die extrusion method or the like and then thermally laminating. A commercially available polyolefin film may be heat laminated. By this heat lamination, the heat seal layer is heated and the transparent resin layer is heat sealed. The heat required for the heat lamination may be appropriately added. When the T-die extrusion method is used, heat brought in when a resin composition containing a polyolefin resin is melt-extruded to form a film may be used. Further, heat lamination (heat sealing) can be performed by heat during embossing described later.

  The transparent resin layer may contain a weathering agent as necessary. As the weathering agent, for example, an ultraviolet absorber, a hindered amine light stabilizer and the like are preferable. These weathering agents can be used alone or in admixture of two or more. In particular, when the transparent resin layer contains polypropylene, it is preferable to contain a weathering agent.

  Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and triazine ultraviolet absorbers. As the light stabilizer, for example, a hindered amine light stabilizer is suitable. The content of these weathering agents is not limited, but both the ultraviolet absorber and the light stabilizer may be about 1000 to 10,000 ppm by mass in the transparent resin layer.

  On the surface of the transparent resin layer, on which the transparent surface protective layer described later is formed, the surface of corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromate treatment, etc., as necessary Processing may be performed. The surface treatment may be performed according to a conventional method for each treatment.

  The thickness of the transparent resin layer is not particularly limited, but is preferably about 10 to 400 μm, more preferably about 40 to 250 μm, and further preferably 40 to 100 μm or more.

  A primer layer (a primer layer for facilitating the formation of the transparent surface protective layer) may be formed on the surface of the transparent resin layer.

  A primer layer can be formed by apply | coating a well-known primer agent to the single side | surface or both surfaces of a base material sheet. Examples of the primer agent include a urethane resin-based primer agent composed of an acrylic-modified urethane resin and the like, and a resin-based primer agent composed of a block copolymer of acrylic and urethane.

Although the thickness of a primer layer is not specifically limited, Usually, 0.1-10 micrometers, Preferably it is about 1-5 micrometers.
(Transparent surface protective layer)
A transparent surface protective layer may be formed on the transparent resin layer. The transparent surface protective layer is not limited, but preferably contains at least one of an ionizing radiation curable resin and a two-component curable urethane resin as a resin component. Substantially those formed from these resins are preferred. When forming a transparent surface protection layer with ionizing radiation curable resin or two-component curable urethane resin, it is easy to improve the abrasion resistance, impact resistance, contamination resistance, scratch resistance, weather resistance, etc. of the decorative sheet. .

  The ionizing radiation curable resin is not particularly limited, and prepolymers (including oligomers) and / or monomers containing radically polymerizable double bonds capable of undergoing a crosslinking reaction upon irradiation with ionizing radiation such as ultraviolet rays and electron beams. A transparent resin containing as a main component can be used. These prepolymers or monomers can be used alone or in combination. The curing reaction is usually a cross-linking curing reaction.

  Specifically, as the prepolymer or monomer, a compound having in the molecule a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group. Is mentioned. Further, a polyene / thiol prepolymer based on a combination of polyene and polythiol is also preferable. Here, the (meth) acryloyl group means an acryloyl group or a methacryloyl group.

  Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. Etc. These molecular weights are usually preferably about 250 to 100,000.

  As a monomer which has a radically polymerizable unsaturated group, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate etc. are mentioned as a monofunctional monomer, for example. Examples of the polyfunctional monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra ( And (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

  Examples of the prepolymer having a cationic polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolac type epoxy compounds, and vinyl ether type resins such as fatty acid type vinyl ethers and aromatic vinyl ethers. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those in which allyl alcohol is added to both ends of polyurethane by diol and diisocyanate.

  As the ionizing radiation used for curing the ionizing radiation curable resin, electromagnetic waves or charged particles having energy capable of causing a curing reaction of molecules in the ionizing radiation curable resin (composition) are used. Usually, ultraviolet rays or electron beams may be used, but visible light, X-rays, ion rays, or the like may be used.

  As the ultraviolet light source, for example, 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, a metal halide lamp can be used. As a wavelength of ultraviolet rays, 190 to 380 nm is usually preferable.

  As the electron beam source, for example, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Among these, those capable of irradiating electrons having energy of 100 to 1000 keV, preferably 100 to 300 keV are preferable.

  Although it is not particularly limited as a two-component curable urethane resin, among them, a polyol component (acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, etc.) having an OH group as a main component and an isocyanate component (tolylene diene) as a curing agent component. Isocyanate, hexamethylene diisocyanate, metaxylene diisocyanate and the like) can be used.

  The transparent surface protective layer may contain an anti-glare agent, a plasticizer, a stabilizer, a filler, a dispersant, a colorant such as a dye and a pigment, a solvent, and the like, if necessary. About the kind in case of containing a weathering agent and content, it is the same as that of the description in a transparent resin layer.

  For example, the transparent surface protective layer is formed by applying an ionizing radiation curable resin or a two-component curable urethane resin on a transparent polypropylene resin layer by a known coating method such as gravure coating or roll coating, and then applying the resin. It can be formed by curing. In the case of an ionizing radiation curable resin, the resin is cured by electron beam irradiation.

The thickness of the surface protective layer is not particularly limited and can be appropriately set according to the characteristics of the final product, but is usually about 0.1 to 50 μm, preferably about 1 to 20 μm.
(Embossing)
The front surface of the decorative sheet may be embossed as necessary.

  The embossing method is not particularly limited. For example, a method of heating and softening the front surface of the transparent surface protective layer and pressurizing and shaping with an embossing plate and then cooling can be mentioned as a preferable method. Depending on the material of a certain decorative sheet or transparent surface protective layer, for example, the front surface of the transparent resin layer is heated and softened, and after pressurizing and shaping with an embossed plate, a transparent surface protective layer is formed thereon. May be.

For embossing, a known single-wafer or rotary embossing machine is used. Examples of the concavo-convex shape include a wood grain plate conduit groove, a stone plate surface unevenness (such as granite cleaved surface), a cloth surface texture, a satin texture, a grain, a hairline, a ridge line, and the like.
(Backer layer made of synthetic resin)
The decorative sheet may have a synthetic resin backer layer on the back surface of the base sheet. Here, the backer layer means a buffer layer for the purpose of shock absorption or the like in the decorative material. Examples of the material constituting the backer layer include polypropylene, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, and high heat-resistant polyalkylene terephthalate [for example, a part of ethylene glycol is 1,4- Polyethylene terephthalate substituted with cyclohexanedimethanol or diethylene glycol, so-called trade name PET-G (manufactured by Eastman Chemical Company)], polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate, poly Examples include arylate, polyimide, polystyrene, polyamide, and ABS. These resins can be used alone or in combination of two or more. The upper limit of the thickness of the backer layer is not limited, but 200 to 600 μm is suitable.

  If necessary, the 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 on the adhesion surface. Further, a primer layer may be further provided on the back surface in consideration of adhesiveness with the adherend.

  By providing the backer layer, the scratch resistance can be improved and the influence of the adherend can be reduced. For example, the effect of unevenness existing on the surface of the adherend can be alleviated, and especially when the adherend is made of wood, the unevenness of polishing formed on the surface during sanding or the knots on the wood (so-called ducts) ) Can be mitigated.

Manufacturing method of decorative sheet The manufacturing method of the decorative sheet of the present invention is not limited as long as it has a predetermined layer structure and the transparent resin layer is bonded by thermal lamination via a heat seal layer, but the following manufacturing method It is preferable that it is manufactured by. That is, on the base material sheet, a method for producing a decorative sheet having a pattern layer, a heat seal layer, and a transparent resin layer containing a polyolefin resin in the order,
(1) A process of forming a pattern layer on a base sheet,
(2) A step of forming a heat seal layer by applying an aqueous emulsion containing a modified polyolefin resin as a dispersoid in a manner covering the pattern layer,
(3) a step of heat-sealing the transparent resin layer by thermally laminating a transparent resin layer containing a polyolefin resin on the heat-seal layer;
It is preferable to manufacture by the manufacturing method characterized by including.

  The components of each layer and the forming method are as described in the section of the decorative sheet. In particular, in the manufacturing method of the present invention, the thermal laminate is formed by melt extrusion of a transparent resin layer on the heat seal layer. It is preferable to be a heat laminate by heat brought in at the time. With such a method, after forming the heat seal layer, the transparent resin layer can be bonded (heat sealed) in-line by heat lamination. Therefore, since the winding and curing steps for curing the adhesive layer are not required as in the conventional product using the adhesive layer or the easy-adhesion resin layer, the decorative sheet is manufactured by a simpler process than the conventional product. be able to.

Cosmetic Material The decorative sheet of the present invention can be made into a cosmetic material by bonding with various adherends. The material of the adherend is not particularly limited, and examples thereof include inorganic non-metallic materials, metallic materials, wood 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 woody system, for example, veneer, plywood, particle board, medium density fiber board (MDF), laminated timber and the like made of cedar, straw, straw, lawan, teak and the like can be mentioned.

  In the plastic system, for example, resin materials such as polypropylene, ABS resin, and phenol resin can be used.

  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.

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

  An adhesive can be used to bond the adherend and the decorative sheet. As an adhesive, for example, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, butadiene-acrylonitrile rubber, neoprene rubber, natural rubber and the like are effective ingredients. Any known adhesive can be used.

  After joining the adherend and the decorative sheet, for example, according to the properties of the final product, cutting, using a tenon, sane processing, V-shaped groove processing, four-side chamfering (for example, C chamfering), etc. You may give it.

  The decorative material of the present invention will be specifically described with reference to FIG.

  The decorative material shown in FIG. 2 includes a back primer layer 12, a base sheet 13, a pattern layer 14, a heat seal layer 15, and a transparent resin layer on an adherend 11 via an adhesive layer (not shown). 16, a primer layer 17 and a surface protective layer 18 are sequentially laminated. Embossing is performed from the surface protective layer side, and a concave embossed portion is attached.

  The decorative sheet of the present invention employs a specific heat seal layer in place of the conventional adhesive layer and easy-adhesion resin layer, and the heat seal layer is a coating formed from an aqueous emulsion containing a modified polyolefin resin as a dispersoid. By being a cured layer of the film, good adhesiveness of the transparent resin layer containing the polyolefin resin is ensured. In addition, the heat seal layer has whitening resistance at the time of bending unlike the conventional easy-adhesion resin layer. Furthermore, since the decorative sheet of the present invention adheres the transparent resin layer by heat sealing, the curing process required when using the conventional adhesive layer is unnecessary and can be easily produced.

It is a schematic diagram (an example) of a decorative material having a conventional easy-adhesive resin layer. It is a schematic diagram (an example) of a decorative material having the heat seal layer of the present invention.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

Example 1
(Production of decorative sheet)
A pattern layer was formed with a printing ink made of a two-component curable acrylic-urethane resin on a 60 μm thick polypropylene base sheet subjected to double-sided corona discharge treatment. Moreover, the primer layer was formed in the base material sheet back surface.

On the pattern layer, a paint composed of an aqueous emulsion of maleic anhydride-modified polypropylene resin was applied so that the solid content was 3 g / m ² to form a heat seal layer.

  A transparent resin layer having a thickness of 60 μm was formed on the heat seal layer by heat-melting and extruding polypropylene resin with a T-die extruder.

Was subjected to corona discharge treatment on the surface of the transparent resin layer, a corona discharge treated surface to acrylic - urethane resin solution surface protective layer formed by coating a solid content of 1 g / m ² by a gravure printing method A primer layer was formed.

An uncured electron beam curable resin layer is formed by applying and drying a urethane acrylate electron beam curable resin on the surface protective layer forming primer layer by a roll coating method so that the solid content becomes 5 g / m ^2. Formed. Then, in an environment with an oxygen concentration of 200 ppm, the uncured resin layer is irradiated with an electron beam under the conditions of an acceleration voltage of 125 KeV and 5 Mrad to cure the resin to form a 5 μm thick electron beam curable resin layer (surface protective layer). did.

From the top of the transparent surface protective layer, a 30-μm deep grain-like uneven pattern was formed by embossing to obtain a decorative sheet.
(Production of decorative board)
A 0.27mm thick coated steel sheet coated with an adhesive composed of a two-component curable urethane resin is cured in an oven at 150 ° C for about 1 minute, and then immediately pasted with the above decorative sheet using a roll laminator, Got.

Example 2
A decorative sheet and a decorative board were produced in the same manner as in Example 1, except that the resin component for forming the pattern layer was a two-component curable vinyl chloride-vinyl acetate-acrylic terpolymer resin.

Example 3
A decorative sheet and a decorative board were produced in the same manner as in Example 1 except that the heat seal layer was formed from a modified polypropylene resin aqueous emulsion and a crosslinking agent.

Example 4
A decorative sheet and a decorative board were produced in the same manner as in Example 1 except that the transparent resin layer was extruded and formed with a polypropylene resin having a polar group.

Example 5
A decorative sheet and a decorative sheet were formed in the same manner as in Example 1 except that a primer layer was formed from a resin composed of acrylic-urethane on the pattern layer and a transparent resin layer composed of a nonpolar polypropylene resin was formed thereon. A decorative board was produced.

Example 6
A decorative sheet and a decorative board were produced in the same manner as in Example 1 except that the transparent resin layer was extruded and formed by blending a polypropylene resin and a polypropylene resin having a polar group in a mass ratio of 8: 2.

Comparative Example 1
A decorative sheet and a decorative board were produced in the same manner as in Example 1 except that the heat seal layer was not formed.

Comparative Example 2
A decorative sheet and a decorative board were formed in the same manner as in Example 1 except that the urethane resin adhesive was applied to the pattern layer so that the thickness after drying was 3 μm, and the heat seal layer was not formed. Was made.

Test example 1: Adhesion test between a transparent resin layer and a substrate sheet (normal test)
Using a Tensilon tester, the transparent resin layer and the base sheet of a normal decorative sheet (25 mm wide) were peeled off at a peeling speed of 100 mm / min, and the load was measured at N = 3 for evaluation. did.

  The evaluation criteria are as follows.

++: 15N or more +: 10N or more but less than 15N −: 0N to less than 9N (environmental test)
The decorative sheet was placed in a constant temperature and high humidity bath at a temperature of 60 ° C. and a humidity of 90% for 2 days, and the adhesion was measured and evaluated in the same manner as in the normal test. The evaluation criteria are as described above.

  The evaluation results of the adhesion test are also shown in Table 1.

Test example 2: Steel sheet bending test (at room temperature)
In accordance with the V-block method specified in JIS Z 2248 6.3, a steel plate bending test was performed under the conditions of a surface temperature of the decorative steel plate of 25 ° C., a bending angle of 90 °, and a bending inner radius of 0 mm.

  The evaluation criteria are as follows.

++: No whitening near the crease ++: Light whitening near the crease −: Whitening or cracking near the crease Table 1 also shows the evaluation results of the steel sheet bending test.

Heat seal layer: Trade name “Aptolock”, Mitsubishi Chemical's transparent resin layer A; Trade name “Prime TPO J5900”, Prime polymer, Random PP
Transparency resin layer B; trade name “Admer QE800”, manufactured by Mitsui Chemicals, maleic acid-modified random PP
Transparent resin layer C: Polypropylene crosslinking agent in which the resin used in transparent resin layers A and B is blended at a mass ratio of 8: 2; trade name “Carbodilite”, manufactured by Nisshinbo Chemical

1. Substrate
2. Primer layer
3. Base sheet
4. Pattern pattern layer
5. Adhesive layer
6. Easy adhesive resin layer
7. Transparent resin layer
8. Primer layer
9. Surface protective layer
11. Substrate
12. Primer layer
13. Base sheet
14. Pattern pattern layer
15. Heat seal layer
16. Transparent resin layer
17. Primer layer
18. Surface protective layer

Claims (13)

On the base sheet, a decorative sheet having a pattern layer, a heat seal layer and a transparent resin layer containing a polyolefin resin in that order,
The heat seal layer, Ri hardened layer der of the coating film formed from an aqueous emulsion comprising a modified polyolefin resin as a dispersoid,
The modified polyolefin resin has a hydrophilic polymer bound thereto,
A decorative sheet characterized by that.   The modified polyolefin resin is made of polyolefin resin, styrene, methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, dichlorostyrene, divinylbenzene, diallylbenzene, divinylnaphthalene, diallylisophthalate, 1,6-hexanediol diacrylate, Selected from the group consisting of methylolpropane triacrylate, pentaerythritol triacrylate, ethylene glycol dimethacrylate, (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, anhydrides of these acids, and monoesters of the acid anhydrides The decorative sheet according to claim 1, wherein at least one of the decorative sheets has a graft polymerized structure. The modified polyolefin resin is a maleic anhydride-modified propylene polymer or a chlorinated product thereof, a maleic anhydride-modified ethylene-propylene copolymer or a chlorinated product thereof, a maleic anhydride-modified propylene-butene copolymer or a chloride thereof, or a maleic anhydride. Acid-modified ethylene-propylene-butene copolymer or its chloride, acrylic acid-modified propylene polymer or its chlorinated product, acrylic acid-modified ethylene-propylene copolymer or its chlorinated product, and acrylic acid-modified propylene-butene copolymer Ri least 1 Tanedea selected from coalescence or the group consisting of the chlorides, the hydrophilic polymer is attached, the decorative sheet according to claim 1. The decorative sheet according to any one of claims 1 to 3, wherein the pattern layer and the transparent resin layer are in direct contact with the heat seal layer, respectively. The hydrophilic polymer, poly (meth) acrylic resins, polyether resins, polyvinyl alcohol resins, at least one selected starch, corn starch, from the group consisting of gelatin and cellulose, one of the claims 1 to 4 decorative sheet according to any.   The decorative pattern according to any one of claims 1 to 5, wherein the pattern layer contains a thermosetting resin.   The decorative sheet according to any one of claims 1 to 6, which has an embossed pattern on the front surface.   The decorative sheet according to any one of claims 1 to 7, further comprising a synthetic resin backer layer on the back surface of the base sheet.   A decorative sheet, wherein the decorative sheet according to any one of claims 1 to 8 is laminated on an adherend through an adhesive layer. On the base sheet, a method for producing a decorative sheet having a pattern layer, a heat seal layer, and a transparent resin layer containing a polyolefin resin in the order,
(1) The process of forming a pattern layer on a base material sheet,
(2) A step of forming a heat seal layer by applying an aqueous emulsion containing a modified polyolefin resin to which a hydrophilic polymer is bonded as a dispersoid in a mode of covering the pattern layer.
(3) A step of heat-sealing the transparent resin layer by thermally laminating a transparent resin layer containing a polyolefin resin on the heat-seal layer,
The manufacturing method characterized by including.   The manufacturing method according to claim 10, wherein the thermal lamination is thermal lamination by heat brought in when the transparent resin layer is melt-extruded and formed on the heat seal layer.   The manufacturing method according to claim 10 or 11, further comprising a step of embossing the front surface. The manufacturing method according to any one of claims 10 to 12, wherein the design pattern layer and the transparent resin layer are in direct contact with the heat seal layer, respectively.

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