JP2015189223A - Decorative sheet, decorative material and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet that is excellent in scratch resistance and dust adhesion-preventing property, and a decorative material, and a production method thereof.SOLUTION: Provided are: a decorative sheet having a surface protective layer on one face of a substrate and having a rear surface primer layer on the other face of the substrate, in which at least one of the surface protective layer and the rear surface primer layer is a resin composition or a hardened product thereof containing an antistatic agent and a resin ingredient comprising a polyether structure; a decorative material; and a production method thereof.

Description

  The present invention relates to a decorative sheet, a decorative material, and a manufacturing method thereof. Specifically, the present invention relates to a decorative sheet, a decorative material, and a method for manufacturing the same, which are excellent in scratch resistance and dust adhesion prevention.

In addition to surface protection properties such as scratch resistance and weather resistance, a decorative sheet for building materials is required to have less dust adhesion due to static electricity during its manufacture and use. As a means for reducing dust adhesion due to static electricity, there is a method of imparting antistatic properties to the decorative sheet.
As a decorative sheet having antistatic properties, an antistatic agent added to any one of various layers constituting the decorative sheet is known. For example, Patent Document 1 discloses a decorative sheet in which a specific antistatic agent is contained in a polypropylene resin layer. Patent Document 2 discloses a decorative sheet containing an antistatic agent in a primer layer in contact with the surface protective layer, and Patent Document 3 discloses a decorative sheet containing an antistatic agent in a surface protective layer. Yes. Patent Document 4 discloses a composition capable of simultaneously achieving antistatic properties and hard coat properties, including an electrolyte having antistatic properties and a monomer, oligomer or prepolymer having hard coat properties, for an image display device or the like. It is disclosed to be applied to a laminate to be used.

  When the antistatic agent is difficult to move in the resin used for each layer constituting the decorative sheet, the antistatic effect may be difficult to be exhibited. In general, it is considered that the antistatic agent is present in an amorphous region in the layer, and it is difficult to obtain a sufficient antistatic effect in a highly crystalline, that is, hard resin layer, and a larger amount of addition is required. (Refer nonpatent literature 1).

JP 2007-261097 A JP 2006-123495 A JP 2008-265301 A JP 2008-274266 A

Edited by Toru Haruna, “Polymer Additive Handbook”, CMC Publishing Co., Ltd., November 7, 2010, p. 134

However, if an antistatic agent is added to the surface protective layer of the decorative sheet and the surface protective layer is too soft in order to give a sufficient antistatic effect, there arises a problem that the scratch resistance is impaired.
An object of the present invention is to provide a decorative sheet, a decorative material, and a method for manufacturing the same, which are excellent in scratch resistance and dust adhesion prevention.

As a result of intensive research in order to solve the above problems, the present inventors have a decorative sheet having a surface protective layer on one surface of a substrate and a back primer layer on the other surface of the substrate. It has been found that the above problem can be solved by using a resin composition containing an antistatic agent and a resin component having a specific structure in at least one of the surface protective layer and the back primer layer.
That is, the present invention provides the following [1] to [4].
[1] A decorative sheet having a surface protective layer on one surface of a base material and a back primer layer on the other surface of the base material, wherein at least one of the surface protective layer and the back surface primer layer is charged A decorative sheet comprising a resin composition comprising an inhibitor and a resin component having a polyether structure or a cured product thereof.
[2] A decorative sheet roll obtained by winding the decorative sheet of [1].
[3] A decorative material in which the decorative sheet of [1] and an adherend are laminated via an adhesive layer.
[4] A method for producing a cosmetic material, comprising a step of bonding the decorative sheet unwound from the decorative sheet roll of [2] and an adherend through an adhesive layer.

  According to the present invention, it is possible to provide a decorative sheet, a decorative material, and a method for manufacturing the same, which are excellent in scratch resistance and dust adhesion prevention. The decorative sheet and the decorative material are useful as a decorative sheet and a decorative material for building materials.

It is a schematic diagram which shows the cross section of an example of the decorative sheet of this invention. It is a schematic diagram which shows the cross section of an example of the decorative material of this invention.

[Layer structure of decorative sheet]
The decorative sheet of the present invention may have any configuration as long as it has at least a surface protective layer on one side of the base material and a back primer layer on the other side of the base material. May be. From the viewpoint of imparting design properties to the decorative sheet, a configuration having a decorative layer and a surface protective layer in order on one side of the base material is preferable, and a decorative layer, a primer layer and a surface protective layer are sequentially provided on one side of the base material. The structure which has is more preferable. In addition, from the viewpoint of imparting weather resistance to the decorative sheet, a configuration having a decorative layer, a transparent resin layer, a primer layer, and a surface protective layer in this order on one surface of the base material is more preferable.
A decorative sheet 10 of the present invention shown in FIG. 1 has a decorative layer 13, a transparent resin layer 15, a primer layer 14, and a surface protective layer 12 in this order on a substrate 11. Moreover, the back surface primer layer 16 is provided on the surface opposite to the surface having the surface protective layer of the substrate 11. In addition, in this specification, the surface opposite to the surface which has the said surface protective layer of the base material 11 is called "the back surface of a decorative sheet."

  The decorative sheet of the present invention is characterized in that at least one of the surface protective layer and the back surface primer layer comprises a resin composition containing an antistatic agent and a resin component having a polyether structure or a cured product thereof. Since the resin having a polyether structure has a high degree of freedom of molecular chain and has hydrophilicity, it is easy to develop antistatic properties when combined with an antistatic agent, and improves dust adhesion preventing property to a decorative sheet. Can do. Therefore, even if the resin composition constituting the surface protective layer or the back primer layer contains an antistatic agent, if the resin composition does not contain a resin component having a polyether structure, sufficient dust adhesion prevention May not develop.

From the viewpoint of obtaining the above effects, the decorative sheet of the present invention is preferably composed of a resin composition in which the surface protective layer and the back primer layer both contain an antistatic agent and a resin component having a polyether structure, or a cured product thereof. . By setting it as this structure, high dust adhesion prevention property can be expressed in each of the surface side and back surface side of a decorative sheet. In addition, even if the amount of the antistatic agent contained in each layer is small, sufficient dust adhesion prevention property can be imparted, so that the surface protective layer has scratch resistance and the adhesion of the back primer layer to the adherend. Easy to maintain. Furthermore, by adopting the above-described configuration, it is possible to suppress the generation of static electricity when the decorative sheet is unwound from the sheet roll obtained by winding the decorative sheet into a roll shape. For example, the makeup unwound from the decorative sheet roll This is also preferable from the viewpoint of production when a decorative material is produced by bonding a sheet and an adherend through an adhesive layer.
Furthermore, from the viewpoint of scratch resistance, dust adhesion prevention, and strength, both the surface protective layer and the back surface primer layer are made of a cured product of a resin composition containing an antistatic agent and a resin component having a polyether structure. It is more preferable.

From the viewpoint of preventing dust adhesion, the decorative sheet of the present invention preferably has a surface resistance value of less than 1.0 × 10 ¹⁴ Ω measured on the front surface and the back surface in accordance with JIS K6911. When the surface resistance value is less than 1.0 × 10 ¹⁴ Ω, dust adhesion prevention due to static electricity is good.
From the viewpoint of imparting sufficient dust adhesion preventing properties to the decorative sheet, the surface resistance value is more preferably 1.0 × 10 ¹³ Ω or less, and further preferably 5.0 × 10 ¹² Ω or less. The lower limit value of the surface resistance value is not particularly limited, but is usually 1.0 × 10 ⁸ Ω or more.
The surface resistance value is a temperature of 20 ° C. and 65% R.S. according to JIS K6911. H. This is a value measured at an applied voltage of 500 V under the above environment, and can be specifically measured by the method described in the examples.
The surface resistance value of the decorative sheet can be controlled by adjusting the content of the antistatic agent in the surface protective layer and the back primer layer, and adjusting the thickness of the surface protective layer and the back primer layer.

[Antistatic agent]
The antistatic agent used in the present invention is not particularly limited, and any of an organic compound antistatic agent, an ionic antistatic agent, and an inorganic solid antistatic agent can be used. Among the antistatic agents, an ionic antistatic agent is preferable from the viewpoint of imparting dust adhesion prevention and an affinity with the resin component.

Examples of organic compound antistatic agents include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene derivatives, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid Nonionic antistatic agents such as esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, alkylalkanol amides and the like can be mentioned.
In addition, a high molecular weight antistatic agent obtained by increasing the molecular weight of the antistatic agent can also be used. Typical examples of the polyether include polyethylene oxide, polyether ester amide, ethylene oxide-epihalohydrin copolymer, methoxypolyethylene glycol (meth) acrylate copolymer, and the like.
Further, a conductive polymer may be used, and specific examples thereof include polyaniline, polyacetylene, polypyrrole, polythiophene, polyvinyl carbazole and the like.

The ionic antistatic agent is preferably at least one selected from alkali metal salts and ionic liquids, and more preferably alkali metal salts.
Alkali metal salts are preferable in that they have high ion dissociation properties and can provide excellent dust adhesion prevention even if the amount used is small. Examples of the alkali metal salt include alkali metal ions such as Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ and Cs ⁺ , halogen ions such as Cl ⁻ , Br ⁻ and I ⁻ , SO ₄ ²⁻ , NO ₃ ⁻ and ClO. Examples of the salt include a combination of ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , various sulfonate ions, acid group ions such as COO ⁻ , or anions such as perchlorate ions.
Further, an alkali metal salt in which the alkali metal ion is incorporated in a matrix having ether oxygen or urethane nitrogen is also preferably used. In the alkali metal salt, ether oxygen or urethane nitrogen constituting the matrix forms a coordination field such as crown ether, and alkali metal ions are incorporated therein. Examples of such alkali metal salts include “Sanconol 0862-20R (lithium salt, adipate)”, “Sanconol PEO-20R (lithium salt, polyol)”, and “Sanconol A600-50R (lithium salt)” manufactured by Sanko Chemical Industry Co., Ltd. Acrylate monomers) ”and the like.
Of these alkali metal salts, lithium salts are preferable from the viewpoint of preventing dust adhesion.

Since the ionic liquid is liquid at room temperature (25 ° C.), it is easier to disperse in the resin composition than the solid salt, and the ionic liquid has no vapor pressure (non-volatile), so it adheres to dust. This is preferable because the preventive property can be continuously obtained. In addition, an ionic liquid refers to the molten salt which exhibits a liquid state at room temperature (25 degreeC).
Examples of the ionic liquid include imidazolium-based, pyridinium-based, quaternary ammonium-based, quaternary phosphonium-based cationic substances, counter ions such as Cl ⁻ , Br ⁻ and I ⁻ halogen ions, SO ₄ ^2- , NO ₃ ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , acid group ions such as various sulfonate ions and COO ^−, and salts (liquids) bonded to anions such as perchlorate ions. .

Further, as ionic antistatic agents other than the above, cationic antistatic agents such as alkylamines and quaternary ammonium salts; fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkylnaphthalene sulfonic acids, alkylsulfosuccinic acid Anionic properties such as salts, alkyl diphenyl ether disulfonates, alkyl phosphates, polyoxyethylene alkylsulfuric acid ester salts, polyoxyethylene alkylallylsulfuric acid ester salts, naphthalenesulfonic acid formalin condensates, carboxylic acid type polymer surfactants, etc. Antistatic agents; and zwitterionic antistatic agents such as alkylbetaines and amine oxides.
In addition, a high molecular weight antistatic agent obtained by increasing the molecular weight of the antistatic agent can also be used. Typical examples of the quaternary ammonium salts include quaternary ammonium base-containing (meth) acrylate copolymers, quaternary ammonium base-containing maleimide copolymers, quaternary ammonium base-containing methacrylic copolymers; Are polystyrene sulfonate sodium; examples of betaines include carbobetaine graft copolymers;

Examples of inorganic solid antistatic agents include particles of inorganic conductive materials, fillers, fibers, and the like. Of these, conductive fibers are preferable in that they can provide high dust adhesion prevention even if the content is small. The conductive fibers preferably have a number average fiber diameter of 0.1 to 1.0 μm and a number average fiber length of 2 to 30 μm.
Inorganic conductive materials include carbon materials such as carbon black, graphite, fullerene, and carbon nanotubes, indium oxide, zinc oxide, tin oxide, potassium titanate, titanium oxide, tin-antimony oxide, and indium-tin oxide. Examples thereof include metal materials such as oxides and antimony-tin oxides. Moreover, what coated the said electroconductive material on the surface of inorganic fiber may be used.

An antistatic agent can be used individually by 1 type or in combination of 2 or more types.
The content of the antistatic agent in the surface protective layer and the back primer layer is preferably 1 to 15 parts by mass, more preferably 2 to 10 parts by mass, and more preferably 100 parts by mass of the resin component contained in each layer. Preferably it is 3-8 mass parts. When the content is 1 part by mass or more, sufficient dust adhesion preventing property is imparted. Moreover, if it is 15 mass parts or less, while being able to maintain the damage resistance of a surface protective layer and the adhesiveness to the adherend of a back surface primer layer, precipitation and bleed-out of an antistatic agent can be avoided.

[Resin component having a polyether structure]
As the resin component having a polyether structure used in the present invention, any resin having at least one polyether structure in the molecule can be used without particular limitation.
Here, “having a polyether structure” means including a structural unit containing a polyether moiety. Examples of the structural unit containing a polyether moiety include a polyether unit such as polyethylene oxide and polypropylene oxide, a polyetherimide unit, a polyetheramide unit, a polyetherester unit, and the like. Two or more kinds may be included. From the viewpoint of imparting high dust adhesion preventing property to the decorative sheet by combination with an antistatic agent, a polyether unit is preferable.
The polyether moiety includes ethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, 1,4-butanediol, 1,9-nonanediol, 1,10-decanediol, 3-methyl. Pentanediol, 2,4-diethylpentanediol, butylethylpropanediol, tricyclodecane dimethanol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanediol, caprolactone Examples thereof include sites derived from various polyether polyols, which are homopolymers or copolymer polymers having diol, hydrogenated bisphenol A, bisphenol A, or the like as monomer units. Of these, a polyether moiety derived from at least one selected from polyethylene glycol and polypropylene glycol is preferred.

  In addition, it is preferable that the resin component which has a polyether structure is curable resin which has a polyether structure from a viewpoint of the scratch resistance of a surface protective layer, and the intensity | strength of a back surface primer layer. That is, it is preferable that at least one of the surface protective layer and the back surface primer layer is made of a cured product of a resin composition containing an antistatic agent and a curable resin having a polyether structure, and the surface protective layer and the back surface primer layer are antistatic. More preferably, it consists of a cured product of a resin composition containing an agent and a curable resin having a polyether structure.

Examples of the curable resin composition include an ionizing radiation curable resin composition and a thermosetting resin composition. The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as γ rays, and charged particle beams such as α rays and ion rays can also be used. The ionizing radiation curable resin refers to a resin (compound) that crosslinks and cures when irradiated with the ionizing radiation.
Among the above, from the viewpoint of imparting scratch resistance, the surface protective layer is preferably made of a cured product of an ionizing radiation curable resin composition or a thermosetting resin composition, and a cured product of the ionizing radiation curable resin composition. More preferably, it consists of the hardened | cured material of an electron beam curable resin composition. Moreover, it is preferable that a back surface primer layer consists of hardened | cured material of a thermosetting resin composition, and it is more preferable that it consists of hardened | cured material of a two-component curable thermosetting resin composition.
Hereinafter, the ionizing radiation curable resin composition and the thermosetting resin composition will be described.

<Ionizing radiation curable resin composition>
In the present invention, the ionizing radiation curable resin composition is a composition containing at least an ionizing radiation curable resin.

[Ionizing radiation curable resin]
The ionizing radiation curable resin used in the present invention can be used without particular limitation as long as it is a compound having at least one ionizing radiation curable functional group. When the ionizing radiation curable resin composition is used for forming the surface protective layer, a polyfunctional compound having two or more ionizing radiation curable functional groups is preferable from the viewpoint of scratch resistance of the surface protective layer.
Here, the ionizing radiation curable functional group is a group that crosslinks and cures upon irradiation with ionizing radiation, and preferably includes a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group. It is done. In the present invention, a (meth) acryloyl group is preferable.

When the ionizing radiation curable resin composition is used for forming a layer containing an antistatic agent, it is preferable to include an ionizing radiation curable resin having a polyether structure as a resin component having a polyether structure (hereinafter referred to as poly The ionizing radiation curable resin having an ether structure is also referred to as “ionizing radiation curable resin (A)”). As described above, since the resin having a polyether structure has a high degree of freedom of molecular chain and hydrophilicity, it easily develops antistatic properties when combined with an antistatic agent, and prevents adhesion of dust to a decorative sheet. Can be improved.
From the viewpoint of improving the dust adhesion prevention property and the scratch resistance of the surface protective layer, the ionizing radiation curable resin having a polyether structure is preferably a urethane (meth) acrylate having a polyether structure, A polyfunctional urethane (meth) acrylate having a polyether structure and having two or more (meth) acryloyl groups is more preferable. The number of functional groups of the polyfunctional urethane (meth) acrylate having a polyether structure may be 2 or more, preferably 2 to 10, more preferably 2 to 6.
In the present invention, two or more ionizing radiation curable resins (A) having the same number of functional groups may be used, or two or more types having different functional groups may be used. Among these, as the ionizing radiation curable resin (A), a trifunctional urethane (meth) acrylate having a polyether structure may be used alone or in combination of two or more, or a bifunctional and hexafunctional urethane having a polyether structure. It is preferable to use a combination of (meth) acrylates.

As the urethane (meth) acrylate having a polyether structure, either a monomer or an oligomer can be used. Examples of the urethane (meth) acrylate monomer or oligomer include those synthesized from polyols having a polyether structure, diisocyanates, and hydroxyl group-containing (meth) acrylate compounds.
The urethane (meth) acrylate oligomer having a polyether structure preferably has a weight average molecular weight (polystyrene equivalent weight average molecular weight measured by GPC method) of 20,000 or less, more preferably 300 to 10,000. More preferably, it is 300-5,000.

  The ionizing radiation curable resin composition used in the present invention may contain only one kind of the ionizing radiation curable resin (A), or may contain two or more kinds. Further, the content of the ionizing radiation curable resin (A) in the ionizing radiation curable resin is preferably 50% by mass or more, more preferably 70% by mass, from the viewpoint of expressing dust adhesion when an antistatic agent is included. As mentioned above, More preferably, it is 90 mass% or more, and an upper limit is 100 mass%.

In addition, when using ionizing radiation curable resin composition for formation of the layer which does not contain an antistatic agent, ionizing radiation curable resin compositions other than the said ionizing radiation curable resin (A) are used for ionizing radiation curable resin composition. A resin (hereinafter also referred to as “ionizing radiation curable resin (B)”) may be used. When the ionizing radiation curable resin composition is used for forming a layer containing an antistatic agent, the ionizing radiation curable resin (B) can be used within a range not impairing the effects of the present invention. The ionizing radiation curable resin (B) is preferably an ionizing radiation curable resin having two or more ionizing radiation curable functional groups from the viewpoint of adjusting the molecular weight between crosslinks of the ionizing radiation curable resin composition.
Such a resin can be appropriately selected from polymerizable monomers and polymerizable oligomers (or prepolymers) conventionally used as ionizing radiation curable resins.

As the polymerizable monomer of the ionizing radiation curable resin (B), other than the ionizing radiation curable resin (A), a polyfunctional (meta) having two or more (meth) acryloyl groups as ionizing radiation curable functional groups in the molecule. ) Acrylate monomers are preferred.
Examples of the polyfunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, dicyclopentanyl di (meth) acrylate, and isocyanurate. Di (meth) acrylates such as di (meth) acrylate; tri (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (acryloxyethyl) isocyanurate; pentaerythritol tetra ( (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acryl Over preparative like 4 or more functional groups of the (meth) acrylate; the above-mentioned polyfunctional (meth) acrylate monomers of ethylene oxide-modified products, propylene oxide-modified products, caprolactone modified products, such as propionic acid-modified products are preferably exemplified. These polyfunctional (meth) acrylate monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

As the polymerizable oligomer of the ionizing radiation curable resin (B), other than the ionizing radiation curable resin (A), a polyfunctional (meta) having two or more (meth) acryloyl groups as ionizing radiation curable functional groups in the molecule. ) Acrylate oligomers. For example, acrylic (meth) acrylate type, epoxy (meth) acrylate type, urethane (meth) acrylate type, polyether (meth) acrylate type other than ionizing radiation curable resin (A), polyester (meth) acrylate type oligomer Preferably mentioned. Furthermore, preferred examples of the polymerizable oligomer include polybutadiene (meth) acrylate oligomers having a (meth) acrylate group in the side chain of the polybutadiene oligomer, and silicone (meth) acrylate oligomers having a polysiloxane bond in the main chain. . These oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.
The number of functional groups of these oligomers is preferably 2 to 16, more preferably 2 to 8, and still more preferably 2 to 6.

  The polymerizable oligomer preferably has a weight average molecular weight (polystyrene equivalent weight average molecular weight measured by GPC method) of 20,000 or less, more preferably 300 to 10,000, and still more preferably 300 to 5, 000.

The ionizing radiation curable resin used in the present invention is preferably electron beam curable. In the case of electron beam curable, solvent-free is possible, which is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator, so that stable curing characteristics can be obtained.
In the ionizing radiation curable resin composition of the present invention, when an ultraviolet curable resin is used as the ionizing radiation curable resin, the photopolymerization initiator is used in an amount of 0.1 to 5 mass with respect to 100 parts by mass of the ultraviolet curable resin. It is desirable to add about a part. The photopolymerization initiator can be appropriately selected from conventionally used photopolymerization initiators, and is not particularly limited. For example, photopolymerization initiators such as benzoin, acetophenone, phenylketone, benzophenone, and anthraquinone Is preferred.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.

  In the ionizing radiation curable resin composition, various additives such as a filler (filler) such as an abrasion resistant filler, a mat forming filler, and a flaw resistant filler, or an ultraviolet absorber (UVA) or a hindered amine for improving weather resistance. A weathering agent such as a light stabilizer (HALS) can be contained. These weathering agents are reactive ultraviolet absorbers having reactive functional groups having ethylenic double bonds such as (meth) acryloyl groups, vinyl groups, and allyl groups, or reactive light stabilizers (HALS). It is preferable from the point that stable weather resistance can be obtained without causing bleeding out of the weathering agent.

<Thermosetting resin composition>
The following thermosetting resin composition is preferably used for forming the back primer layer and the like in the decorative sheet of the present invention.

[Thermosetting resin]
Examples of the thermosetting resin contained in the thermosetting resin composition include vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, alkyd resin, A nitrocellulose resin, a cellulose acetate resin, etc. are mentioned preferably, Moreover, 2 liquid curable resin containing a main ingredient and a hardening | curing agent is also mentioned preferably. Among these, a two-component curable resin is preferable as the thermosetting resin because excellent adhesion to a substrate, an adherend, and the like can be obtained.
The two-component curable resin contained in the two-component curable resin composition is not particularly limited as long as it is a resin that is cured by adding a curing agent to the main agent, and the main agent is a polyol (polyhydric alcohol). A two-component curable urethane resin in which is an isocyanate curing agent is preferred.

  Examples of the main agent include polyols such as butylene glycol and 1,6-hexanediol, polyether polyols such as polyethylene glycol and polypropylene glycol; (meth) acrylic esters such as methyl (meth) acrylate, and (meth ) Acrylic polyols obtained by addition polymerization with monomers having hydroxyl groups such as 2-hydroxyethyl acrylate and 2-hydroxypropyl (meth) acrylate; known diols, for example, glycols such as ethylene glycol and propylene glycol A polyester polyol obtained by a polycondensation reaction with at least one selected from dibasic acids such as adipic acid, maleic acid, phthalic acid, terephthalic acid, and acid esters thereof; Urethane acrylic polyol obtained by reacting an isocyanate compound; said diols with ethylene oxide, propylene oxide, obtained by addition polymerization of such as tetrahydrofuran, a polyol having a hydroxyl group as the functional group; and the like preferably. These can be used alone or in combination of two or more.

  As the isocyanate curing agent, a conventionally known compound may be used as appropriate, for example, aromatics such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate. Isocyanate or poly, such as 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Isocyanates are used. Further, adducts or multimers of these various isocyanates, for example, adducts of tolylene diisocyanate, tolylene diisocyanate trimers, and the like are also used.

  The amount of the curing agent used is preferably 1 to 50 parts by weight, more preferably 3 to 50 parts by weight, still more preferably 3 to 30 parts by weight, particularly preferably 100 parts by weight of the main agent. 3 to 20 parts by mass. When the amount of the curing agent used is within the above range, a good cured state can be obtained, so that excellent adhesion can be obtained, and excellent workability can be obtained in which no cracks are generated during bending.

  Here, when the thermosetting resin composition is used for forming a layer containing an antistatic agent, the thermosetting resin composition is a thermosetting resin having a polyether structure (hereinafter, thermosetting having a polyether structure). It is preferable that the curable resin also includes “thermosetting resin (A)”. As the thermosetting resin (A), a two-component curable resin containing the aforementioned polyether polyol and an isocyanate curing agent is preferable.

  The said thermosetting resin composition may contain only 1 type of the said thermosetting resins (A), and may contain 2 or more types. Further, the content of the thermosetting resin (A) in the thermosetting resin is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more, from the viewpoint of preventing dust adhesion. Yes, the upper limit is 100% by mass.

  The thermosetting resin composition also includes various additives such as anti-wear fillers, mat-forming fillers, scratch-resistant fillers, etc., or ultraviolet absorbers (UVA) and hindered amines for improving weather resistance. Weathering agents such as light stabilizers (HALS) can be included.

(Base material)
In the decorative sheet of the present invention, the base material 11 is selected in consideration of suitability for post-processing, and typically a resin film made of a thermoplastic resin is used. As the thermoplastic resin, generally used are polyolefin resins such as polypropylene and polyethylene, polycarbonate resin, acrylonitrile-butadiene-styrene resin (hereinafter referred to as “ABS resin”), acrylic resin, vinyl chloride resin, and the like. The Among these, polyolefin resins, polycarbonate resins, and ABS resins are preferable. Particularly, in the decorative sheet, polyolefin resins are preferable.
It does not specifically limit as polyolefin resin, What is normally used in the field | area of a 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.
Moreover, the said base material can also use the single layer film of the said resin, or the multilayer film by the same kind or different resin.
Although the thickness of the said base material is selected according to a use, it is preferable that it is 20-150 micrometers from viewpoints, such as workability, a softness | flexibility, and an intensity | strength, and it is more preferable that it is 30-120 micrometers.

  An additive may be blended in the base material as necessary. 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. The blending amount of the additive can be appropriately set according to the product characteristics.

In the present invention, the substrate is preferably colored. As a result, it is possible to hide the adherend of the decorative material described later, or to adjust the surface color when there is color unevenness.
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, 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 substrate includes transparent coloring and opaque coloring (hiding coloring), and these can be arbitrarily selected. For example, when the ground color of an adherend such as a steel plate to which a decorative sheet is attached is colored and concealed, opaque coloring may be selected. On the other hand, in order to make the ground pattern of an adherend such as a steel plate used in the decorative material of the present invention visible, transparent coloring may be selected.
The base material is subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides, if desired, in order to improve the adhesion to the decorative layer or the back surface primer layer provided on the base material. Can do.
Examples of the oxidation method include corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include sand blast method and solvent treatment method. It is done. These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
In addition, the base material 11 may be subjected to primer treatment, or may be preliminarily formed with a paint for adjusting the color or a pattern from a design viewpoint.

(Surface protective layer)
In the decorative sheet of the present invention, the surface protective layer 12 is provided for imparting scratch resistance to the decorative sheet. As described above, the surface protective layer is preferably made of a cured product of an ionizing radiation curable resin composition or a thermosetting resin composition, more preferably a cured product of an ionizing radiation curable resin composition, and an electron beam. More preferably, it consists of the hardened | cured material of curable resin composition. The curable resin composition described above can be used as the curable resin composition.
In addition, when a surface protective layer contains an antistatic agent, the material which forms a surface protective layer contains the resin component which has the polyether structure mentioned above from a viewpoint of expressing dust adhesion prevention property.
From the viewpoint of imparting particularly good scratch resistance and dust adhesion prevention properties to the decorative sheet, the surface protective layer comprises an ionizing radiation curable resin containing the above-described antistatic agent and urethane (meth) acrylate having a polyether structure. It is particularly preferable that the composition consists of a cured product.

In the decorative sheet of the present invention, the thickness of the surface protective layer is preferably 2 to 18 μm. When the thickness of the surface protective layer is 2 μm or more, dust adhesion prevention and scratch resistance are good. On the other hand, if the thickness of the surface protective layer is 18 μm or less, the processability of the decorative sheet is good.
Further, the thickness of the surface protective layer is more preferably 2 to 15 μm, and further preferably 3 to 10 μm, from the viewpoint of providing a good balance between dust adhesion prevention, scratch resistance and workability.

(Back primer layer)
The decorative sheet of the present invention has a back primer layer 16 on the other surface (back surface) of the substrate 11. The back primer layer is provided for the purpose of improving the adhesiveness to the adherend when the decorative material 20 described later is formed.
The material for forming the back primer layer is not particularly limited, and may be appropriately selected depending on the adherend to be deposited, but is preferably the thermosetting resin composition described above. More preferably, it is a two-component curable thermosetting resin composition.
In addition, when a back surface primer layer contains an antistatic agent, the material which forms a back surface primer layer contains the resin component which has the polyether structure mentioned above from a viewpoint of expressing dust adhesion prevention property.
From the viewpoint of imparting particularly good dust adhesion prevention properties to the decorative sheet, the back primer layer is a cured product of a two-component curable resin composition containing the above-described antistatic agent, polyether polyol, and isocyanate curing agent. It is particularly preferred that

  The thickness of the back primer layer is preferably about 0.5 to 5 μm, more preferably 1 to 3 μm. When the thickness is within the above range, excellent performance as a primer layer can be obtained. Further, when the back primer layer contains an antistatic agent and a resin component having a polyether structure, the dust adhesion preventing property is good when the thickness is within the above range.

(Decoration layer)
The decorative sheet 10 of the present invention may be provided with a decorative layer 13 between the base material 11 and the surface protective layer 12 as desired. The decorative layer 13 shown in FIG. 1 gives decorativeness to the decorative sheet. The decorative layer 13 may be a colored layer (solid printing layer) that is uniformly colored, or a variety of patterns using ink and a printing machine. It may be a pattern layer formed by printing. Moreover, you may combine a colored layer and a pattern layer.

From the viewpoint of design, the colored layer is provided for the purpose of concealing the base material such as the adherend on which the base material or the decorative sheet is provided. It is a layer that can adjust the color of the surface by giving. The colored layer is formed of a resin composition containing a binder resin and a colorant.
As said binder resin, the thermosetting resin composition mentioned above is mentioned as a preferable thing. In addition to the concealing function, a two-part curable resin is preferable because excellent adhesion to a substrate and the like can be obtained. That is, the colored layer is preferably composed of a cured product of a two-component curable resin composition containing a two-component curable resin and a colorant.
The two-component curable resin contained in the two-component curable resin composition is not particularly limited as long as it is a resin that is cured by adding a curing agent to the main agent, and the main agent is a polyol (polyhydric alcohol). A two-component curable urethane resin in which is an isocyanate curing agent is preferred.

  Of the two-component curable resins, a two-component curable urethane resin in which the main agent is a urethane acrylic polyol and the curing agent is an isocyanate curing agent is particularly preferable. By adopting the resin, excellent adhesion can be obtained.

Preferred examples of the colorant contained in the resin composition forming the colored layer include those exemplified as the colorant contained in the substrate. The colored layer is usually formed with an opaque color for the purpose of concealing the substrate and the base, but it can also be formed with a colored transparent color to make use of the pattern that the substrate has. Just choose.
The content of the colorant is not particularly limited as long as the color layer concealing function and the adhesion to the substrate are ensured and the applicability of the resin composition is not impaired.

  Moreover, the resin composition which forms a colored layer can contain an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a hardening | curing agent, etc. suitably as needed.

  The thickness of the colored layer is usually about 0.5 to 20 μm, preferably 1 to 10 μm. If it is this range, the design property excellent in the decorative sheet can be provided, and shrinkage | contraction in a manufacture process does not arise.

The pattern layer is also formed of a resin composition containing a binder resin and a colorant.
The patterns that make up the pattern layer include wood grain patterns, marble patterns (for example, travertine marble patterns), stone patterns simulating the surface of rocks, fabric patterns simulating cloth and cloth patterns, tiled patterns, and brickwork There are patterns, etc., and there are also patterns such as marquetry and patchwork that combine these. These patterns are formed by multicolor printing with normal yellow, red, blue, and black process colors, as well as by multicolor printing with special colors prepared by preparing individual color plates that make up the pattern. Is done.
There is no restriction | limiting in particular as a resin composition used for formation of a pattern layer, For example, the resin composition used for formation of a colored layer is mentioned preferably.

  The thickness of the pattern layer is usually about 0.5 to 20 μm, preferably 1 to 10 μm. If it is this range, the design property excellent in the decorative sheet can be provided, and shrinkage | contraction in a manufacture process does not arise.

(Primer layer)
The decorative sheet 10 of the present invention may be provided with a primer layer 14 between the decorative layer 13 and the surface protective layer 12. By providing the primer layer, the adhesion between the surface protective layer and the layer in contact with the surface protective layer can be enhanced.

The material for forming the primer layer 14 is not particularly limited, but is preferably the aforementioned two-part curable resin composition containing a main agent and a curing agent.
The primer layer can be formed using a known printing method, coating method, or the like, using the resin composition as it is or in a state of being dissolved or dispersed in a solvent.

  The thickness of the primer layer 14 is usually about 0.1 to 10 μm, and preferably 0.5 to 5 μm. When the thickness of the primer layer 14 is within the above range, excellent adhesion can be obtained.

(Transparent resin layer)
A transparent resin layer 15 may be formed between the decorative layer 13 and the primer layer 14 for the purpose of imparting various performances such as scratch resistance and weather resistance. The transparent resin layer 15 is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and translucent. The resin component forming the transparent resin layer is preferably a film made of a polyolefin-based resin such as polypropylene, among those exemplified above as the base resin. More preferably, it is a polyolefin resin film having stereoregularity. When using a polyolefin resin, it is desirable to form a transparent resin layer by an extrusion method using a molten polyolefin resin.
For the transparent resin layer, if necessary, a filler, matting agent, foaming agent, flame retardant, lubricant, antistatic agent, antioxidant, ultraviolet absorber, light stabilizer, radical scavenger, soft component ( For example, various additives such as rubber) may be included.
Examples of the method for forming the transparent resin layer include a method of laminating a resin composition containing the above resin component on the decorative layer (or adhesive layer) by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like. It is done.
Although the thickness of a transparent resin layer is not specifically limited, Generally, it is about 20-250 micrometers, and it is preferable to set it as 30-200 micrometers.
The surface of the transparent resin layer on which the surface protective layer is formed may be subjected to a surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, or dichromic acid treatment as necessary. The surface treatment may be performed according to a conventional method for each treatment.

(Uneven pattern)
The decorative sheet of the present invention can be provided with a concavo-convex pattern on the surface thereof from the viewpoint of improving the concavo-convex feeling and texture. For example, when the pattern layer exhibits a wood grain pattern, it is possible to express a wood grain pattern with an excellent texture by synchronizing the wood grain pattern conduit portion with the uneven pattern. Also, for example, when the pattern layer exhibits a tiled pattern, the jointed groove part visually becomes a concave part by synchronizing the tiled joint groove part and the concavo-convex pattern. Is obtained.

[Method for producing decorative sheet]
In the decorative sheet shown in FIG. 1, for example, a decoration layer 13 is formed on a base material 11, and then a transparent resin layer 15 is formed on the decoration layer 13. Subsequently, it can manufacture by passing through the process of forming the primer layer 14 on the transparent resin layer 15, and forming the surface protective layer 12 on this primer layer in order.
The back primer layer 16 may form the back primer layer 16 on the substrate 11 in advance, and then sequentially form each layer such as the decorative layer 13 on the opposite surface, or after forming the surface protective layer 12, A reverse primer layer 16 may be formed on the opposite surface. Further, the back primer layer 16 may be formed on the substrate 11 before or after the transparent resin layer 15 is formed.

First, a resin sheet used for the substrate 11, for example, a polyolefin resin composition in which a colorant and other additives are added to a polyolefin resin as required, a method such as a calendar method, an inflation method, a T-die extrusion method, etc. To make a sheet. The sheet may be biaxially stretched as necessary.
Moreover, the base material 11 can also perform physical or chemical surface treatments, such as said oxidation method and uneven | corrugated method, on the single side | surface or both surfaces.

The method for forming the decorative layer (colored layer and pattern layer) is not particularly limited. For example, the colored layer is a resin composition used for forming the above-described colored layer, 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, What is necessary is just to form using various coating methods, such as a dip coat method.
In addition, the pattern layer is formed by applying the resin composition used for forming the pattern layer described above by various methods such as gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing. To be formed. 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 partial vapor deposition method such as metal, the etching method, etc. may be used or used in combination with other forming methods. Good.

  The back primer layer 16 may be formed by appropriately selecting and applying the resin composition for forming the back primer layer from the forming methods exemplified as the forming method of the colored layer and the pattern layer.

  Next, the transparent resin layer 15 is formed on the decoration layer 13. As a method of forming the transparent resin layer 15, a thermal lamination provided by heating and pressurizing a sheet-shaped transparent resin film, or a thermoplastic resin composition for forming a transparent resin layer using a T-die extruder is used. An EC coat that heats and melts, flows down on the decorative layer 13, and is sandwiched between a rubber roll and a cooled metal roll, thereby forming the transparent resin layer 15 and bonding and laminating on the decorative layer 13. The method etc. are mentioned preferably.

Next, the primer layer 14 is formed on the transparent resin layer 15, and the surface protective layer 12 is formed on the primer layer. The primer layer 14 is formed by applying a resin composition forming the primer layer 14 by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method. be able to.
The surface protective layer 12 is formed by applying a curable resin composition containing a curable resin such as the above-mentioned ionizing radiation curable resin or thermosetting resin on the primer layer 14, and a curing method suitable for the resin composition to be used. Can be formed by curing the resin composition.

  For example, when the surface protective layer 12 is a cured product of an ionizing radiation curable resin composition, the primer layer is applied so that the thickness after curing is preferably 2 to 18 μm. 14 is a known method such as a gravure printing method, bar coating method, roll coating method, reverse roll coating method or comma coating method, preferably a gravure printing method. The viscosity of the ionizing radiation curable resin composition is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer by various methods.

Next, the uncured resin layer formed by applying the ionizing radiation curable resin composition is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer, and the ionizing radiation curable resin composition The surface protective layer 12 that is a cured product of is formed.
When an electron beam is used as the ionizing radiation, the accelerating voltage can be appropriately selected according to the resin used and the thickness of the layer, but it is preferable to cure the uncured resin layer usually at an accelerating voltage of about 70 to 300 kV.

In electron beam irradiation, transmission capability increases as the acceleration voltage increases. Therefore, when using a material that deteriorates due to electron beams as a base material or transparent resin layer, the transmission depth of the electron beam and the thickness of the resin layer are By selecting the accelerating voltage so as to be substantially equal, it is possible to suppress irradiation of extra electron beams on the base material, and to minimize deterioration of the base material due to excess electron beams.
The irradiation dose is preferably such that the crosslinking density of the uncured resin layer is saturated, usually 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 100 kGy (1 to 10 Mrad), more preferably 30 to 70 kGy (3 to 3). 7Mrad).
The electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft 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.

  When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

  Moreover, when providing a concavo-convex pattern on the decorative sheet surface, the method of forming the concavo-convex pattern is not particularly limited, but embossing using an embossed plate or a shaping sheet, or a transfer sheet having a layer having a concavo-convex pattern is provided. And a method of imparting a concavo-convex pattern by transferring a layer having a concavo-convex shape. In the present invention, it is preferable to use embossing from the viewpoint of productivity, and further embossing using an embossed plate is preferable.

  As the embossing, usually an embossing method by heating and pressurization using an embossed plate is preferably used. In the embossing method by heating and pressing, the surface on the surface protective layer side of the decorative sheet is usually heated at about 130 to 180 ° C., and the embossed plate is pressed to shape the uneven pattern of the embossed plate, cooled and fixed. A known sheet-fed or rotary embossing machine can be used.

[Decorative sheet roll]
The decorative sheet roll of the present invention is a roll of the decorative sheet of the present invention. In the decorative sheet of the present invention, at least one of the surface protective layer and the back surface primer layer is composed of a resin composition containing an antistatic agent and a resin component having a polyether structure or a cured product thereof, so that it can prevent dust adhesion. In addition to being excellent, it is also possible to suppress the generation of static electricity during winding and unwinding. The decorative sheet roll is preferably used in a method for continuously unwinding a decorative sheet to produce a decorative material.

[Cosmetic materials]
The decorative material of the present invention is obtained by laminating the decorative sheet of the present invention and an adherend through an adhesive layer. FIG. 2 is a schematic view showing a cross section of an example of the decorative material of the present invention. For example, the back surface of the decorative sheet 10 of the present invention and the adherend 17 are bonded together via an adhesive layer 18. The decorative material 20 can be obtained.

(Substrate)
The adherend 17 is not particularly limited, and a plastic sheet, a metal plate such as a steel plate, a wooden board such as wood, a ceramic material, or the like can be appropriately selected according to the application. When using these adherends, especially plastic sheets as adherends, physical or chemical methods such as an oxidation method or an unevenness method may be applied to one or both sides as desired in order to improve the adhesion to the decorative sheet. Surface treatment can be performed. As specific examples of the oxidation method and the unevenness method, the same methods as described above can be used.
Moreover, as a metal used for a steel plate, metal materials, such as iron, aluminum, copper, are mentioned, These may be surface-treated, such as a hot dip galvanization process and an electrogalvanization process. The shape of the adherend is not particularly limited, and for example, shapes such as a flat plate, a curved plate, and a polygonal column can be arbitrarily adopted.
Moreover, although there is no restriction | limiting in particular about the thickness of a to-be-adhered material, Usually, it is about 0.2-1 mm. In addition, in order to provide concealability, a coating layer may be provided by coloring the adherend directly.

(Adhesive layer)
The adhesive constituting the adhesive layer 18 for bonding the decorative sheet 10 and the adherend 17 is not particularly limited, and an epoxy-based adhesive, a urethane-based adhesive, a polyester-based adhesive, or the like can be suitably used. .
Although there is no restriction | limiting in particular about the thickness of an adhesive bond layer, Usually, it is about 0.1-200 micrometers.

[Manufacturing method of cosmetic material]
The manufacturing method of the decorative material of the present invention includes a step of bonding the decorative sheet unwound from the above-described decorative sheet roll and the adherend through an adhesive layer.
In the above step, for example, an adhesive constituting the adhesive layer 18 is applied to the back surface of the decorative sheet, and after heating and drying as necessary, makeup is performed via the adhesive layer formed by the adhesive. The sheet is continuously adhered to the surface portion of the adherend. For example, a flat sheet material and a decorative sheet unwound from a sheet roll are supplied to a conveyor device such as a belt conveyor, and an adhesive is continuously applied to the decorative sheet, and then a roller (also used as a crimping jig) is used. The decorative sheet and the adherend can be bonded together.
Since the decorative sheet of the present invention has the above-described configuration, it is excellent in dust adhesion prevention even in the production of the decorative material, and can also suppress the generation of static electricity when unwinding from the sheet roll, and is excellent in handleability.

You may perform the process of bending the edge part of a decorative sheet after the said process, and sticking a decorative sheet on the side part and back surface of a to-be-adhered material through an adhesive bond layer.
Further, the process of cutting the decorative sheet along the side surface of the adherend in a direction orthogonal to the flow direction of the adherend, or cutting the decorative sheet together with the adherent in a direction orthogonal to the flow direction of the adherend May be performed. The former is a case where the adherend is already cut to a required size, and cuts the decorative sheet along the side face of the adherend. In the latter case, the adherend is cut to a required size, and at the same time, the decorative sheet attached to the adherend is cut.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the various characteristics of the decorative sheet obtained in each example were evaluated according to the following procedures.

<Surface resistance value>
Measurement was performed using a digital super insulation / microammeter manufactured by Hioki Electric Co., Ltd. According to JIS K6911, temperature 20 ° C., 60% R.D. H. Under the environment, a voltage of 500 V was applied to the decorative sheet obtained in each example, and the value after 10 seconds was read.

<Dust adhesion to front and back>
The front and back surfaces of the decorative sheet obtained in each example were rubbed 10 times with nylon fibers and then sprinkled with finely cut wool fibers. After dropping the wool fibers with the decorative sheet placed vertically, the amount of the wool fibers remaining on the decorative sheet was visually evaluated based on the following criteria with reference to Comparative Example 1 (no antistatic agent added).
(Double-circle): There was no residual wool fiber. Surface resistance value: 1.0 × 10 ¹¹ Ω or less ○: Residual amount of wool fibers was slight. Surface resistance value: more than 1.0 × 10 ¹¹ Ω, 1.0 × 10 ¹² Ω or less Δ: The residual amount of wool fibers was smaller than that in Comparative Example 1. Surface resistance value: more than 1.0 × 10 ¹² Ω, less than 1.0 × 10 ¹⁴ Ω ×: Residual amount of wool fibers was about the same as in Comparative Example 1. Surface resistance value: 1.0 × 10 ¹⁴ Ω or more

<Scratch resistance>
A rubbing test was carried out 10 times with a load of 300 g / m ² using “Bonster # 0000” manufactured by Nippon Steel Wool Co., Ltd. on the surface protective layer surface of the decorative sheet obtained in each example. The surface protective layer after the test was visually evaluated according to the following criteria.
○: There was no scratch and the change in gloss was slight.
(Triangle | delta): Although there was a damage, the gloss change was slight.
X: There was a flaw and the gloss change was remarkable.

Example 1 (Manufacture of decorative sheet)
As the base material 11, a colored polypropylene resin film having a thickness of 60 μm and subjected to corona discharge treatment on both surfaces was prepared. A two-component curable polyether structure-containing urethane resin (main agent; polyether polyol, curing agent; hexamethylene diisocyanate, curing agent 5 parts by mass with respect to 100 parts by mass of the main agent) is applied to the back surface of the substrate, and the temperature is 50. The back primer layer 16 having a thickness of 1.5 μm was formed by thermosetting at a temperature of 0 ° C.
Next, a colored layer and a woodgrain pattern layer were formed in order on the surface of the substrate 11 by gravure printing to form a decoration layer 13. As the binder resin, a two-component curable urethane resin composed of a urethane acrylic polyol and a hexamethylene diisocyanate curing agent was used for the colored layer, and a urethane acrylic polyol resin was used for the pattern layer.
Next, a transparent resin film (thickness 40 μm) obtained by melting a polypropylene-based thermoplastic elastomer with a T-die was laminated on the decorative layer to form a transparent resin layer 15. After subjecting the surface of the transparent resin layer to corona discharge treatment, a primer layer 14 having a thickness of 1 μm was formed by gravure printing using a thermosetting resin composition for forming a primer layer, which is a two-component curable urethane resin.
Furthermore, on the primer layer 14, the resin composition for surface protection layers which is an ionizing radiation curable resin composition of the composition shown in Table 1 was applied by a roll coater method to form an uncured resin layer. Next, the uncured resin layer was cured by irradiating an electron beam under the condition of 165 keV / 5 Mrad (50 kGy) to form a surface protective layer 12 having a thickness of 5 μm. An embossing process was formed on the surface protective layer by embossing to obtain a grained decorative sheet 10 having a grain pattern. Table 1 shows the results of the decorative sheet evaluated by the above method.

Examples 2-3 and Comparative Examples 1-3
In Example 1, a decorative sheet was obtained in the same manner as in Example 1 except that the resin compositions for the surface protective layer and the back surface primer layer were changed as shown in Table 1, respectively. The results evaluated in the same manner as in Example 1 are shown in Table 1.

Details of the components shown in Table 1 are as follows.
<Resin composition for surface protective layer>
-Polyether structure-containing urethane acrylate: 2-6 functional urethane acrylate having a polyether structure-Acrylic acrylate: 2-6 functional acrylic acrylate oligomer having no polyether structure-Antistatic agent: acrylate monomer lithium salt (3 "Sanconol A600-50R" manufactured by Photochemical Industry Co., Ltd.)
<Resin composition for backside primer layer>
-Polyether structure-containing urethane resin: Two-part curable urethane resin having a polyether structure (main agent: polyether polyol, curing agent: hexamethylene diisocyanate, curing agent 5 parts by mass with respect to 100 parts by mass of the main agent)
Polyester urethane resin: Two-component curable polyester urethane resin having no polyether structure (main agent: polyester polyol, curing agent: hexamethylene diisocyanate, curing agent 5 parts by mass with respect to 100 parts by mass of the main agent)
Antistatic agent: acrylate monomer lithium salt (“Sanconol A600-50R” manufactured by Sanko Chemical Co., Ltd.)

From the results shown in Table 1, the decorative sheets of Examples 1 to 3 had dust adhesion preventing properties and good scratch resistance. In particular, as shown in Example 3, when both the resin composition forming the surface protective layer and the back surface primer layer contain an antistatic agent and a resin component having a polyether structure, the dust adhesion prevention property is particularly excellent. It became a decorative sheet.
In contrast, Comparative Example 1 in which neither the surface protective layer nor the back surface primer layer contains an antistatic agent, and the resin composition that forms the layer containing the antistatic agent is a resin component that does not have a polyether structure. Both of the decorative sheets of Comparative Examples 2 and 3 containing Inferior were inferior in dust adhesion prevention.

  According to the present invention, it is possible to provide a decorative sheet, a decorative material, and a method for manufacturing the same, which are excellent in scratch resistance and dust adhesion prevention. The decorative sheet and the decorative material are useful as a decorative sheet and a decorative material for building materials.

DESCRIPTION OF SYMBOLS 10 Cosmetic sheet 11 Base material 12 Surface protection layer 13 Decoration layer 14 Primer layer 15 Transparent resin layer 16 Back surface primer layer 17 Adhering material 18 Adhesive layer 20 Cosmetic material

Claims (9)

  A decorative sheet having a surface protective layer on one surface of a substrate and having a back primer layer on the other surface of the substrate, wherein at least one of the surface protective layer and the back primer layer is an antistatic agent A decorative sheet comprising a resin composition containing a resin component having a polyether structure or a cured product thereof.   The decorative sheet according to claim 1, wherein at least one of the surface protective layer and the back primer layer is formed of a cured product of a resin composition containing an antistatic agent and a resin component having a polyether structure.   The decorative sheet according to claim 1 or 2, wherein the surface protective layer comprises a cured product of an ionizing radiation curable resin composition or a thermosetting resin composition.   The decorative sheet according to any one of claims 1 to 3, wherein the back primer layer comprises a cured product of a thermosetting resin composition.   The surface protective layer comprises a cured product of an ionizing radiation curable resin composition containing an antistatic agent and a urethane (meth) acrylate having a polyether structure, and the back primer layer is an antistatic agent, a polyether polyol, The decorative sheet according to any one of claims 1 to 4, comprising a cured product of a two-component curable resin composition containing an isocyanate curing agent.   The decorative sheet according to any one of claims 1 to 5, comprising a decorative layer, a transparent resin layer, a primer layer, and the surface protective layer in this order on one surface of the substrate.   The decorative sheet roll which wound up the decorative sheet in any one of Claims 1-6.   A decorative material in which the decorative sheet according to any one of claims 1 to 6 and an adherend are laminated via an adhesive layer.   A method for producing a cosmetic material, comprising a step of bonding a decorative sheet unwound from the decorative sheet roll of claim 7 and an adherend through an adhesive layer.