JP6136457B2 - Cosmetic material - Google Patents

Description

  The present invention relates to a decorative sheet and a decorative material using the decorative sheet, and more particularly to a decorative material in which a groove or a chamfered portion is colored and a decorative sheet suitable for manufacturing the decorative material.

  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. For example, Patent Document 1 states that “a flooring decorative sheet having a pattern layer and a surface protective layer in order on a hard film having a thickness of at least 100 to 500 μm, and measured according to the provisions of JIS K6734 for hard films. The decorative sheet for flooring in which the tensile modulus of elasticity is 1000 MPa or more and the hard film contains a polyolefin resin as a resin component is disclosed.

  The olefin-based decorative sheet is laminated on various adherends and used as a decorative material. Depending on the application, the decorative material is provided with a groove portion and a chamfered portion (a V-shaped groove and an end C chamfered portion). The cross section of the olefin-based decorative sheet in the groove and the chamfered portion becomes conspicuous, and the design properties of the decorative material may be impaired.

  In order to prevent the design of the cosmetic material from deteriorating due to the conspicuous cross section of the olefinic decorative sheet, the groove and chamfered part of the decorative material may be painted with colored paint, but the colored paint is in close contact with the cross section of the olefinic decorative sheet. It is hard to do. Therefore, in order to improve the adhesion of the colored paint, the cross section is subjected to corona treatment.

  However, since a large-scale facility is required to perform the corona treatment, it is desired to improve the adhesion of the colored paint without depending on the corona treatment. An example of a method for improving the adhesion of the colored paint without depending on the corona treatment is to add an easily adhesive resin to the polyolefin decorative sheet. Examples of the easy-adhesion resin include acid-modified polypropylene, but a relatively large amount of easy-adhesion resin must be added in order to ensure sufficient adhesion of the colored paint. Therefore, there is a problem that the olefin-based decorative sheet is easily whitened when bent. Moreover, when an easily adhesive resin is added to the synthetic resin backer layer, the impact resistance may be reduced.

  Therefore, the development of an olefin-based decorative sheet in which the adhesion of the colored paint to the cross section of the decorative sheet is improved without using a corona treatment and an easily adhesive resin is desired.

JP 2011-052537 A

  An object of the present invention is to provide an olefin-based decorative sheet in which the adhesion of a colored paint to a cross-section of a decorative sheet is improved without using a corona treatment and an easily adhesive resin. Another object of the present invention is to provide a cosmetic material using the olefin-based decorative sheet.

  As a result of intensive studies, the present inventors have found that the above object can be achieved when a specific resin component is added to the olefin-based decorative sheet, and have completed the present invention.

That is, the present invention relates to the reduction粧材below.
1. A decorative material in which a decorative sheet is laminated on an adherend via an adhesive layer,
The decorative material has a groove portion and / or a chamfered portion from the decorative sheet side to the adherend, and the groove portion and the chamfered portion are painted with a colored paint,
The decorative sheet has one or more layers laminated on one side or both sides of the base sheet ,
(1) At least one of the layers constituting the decorative sheet contains a polyolefin resin and a silane-modified polyolefin resin,
(2) The content of the silane-modified polyolefin resin is 10% by mass or more when the total amount of the polyolefin resin and the silane-modified polyolefin resin is 100% by mass.
A cosmetic material characterized by that.
2. Item 2. The cosmetic material according to Item 1, wherein the silane-modified polyolefin resin has a structure in which 0.5 to 20 parts by mass of an unsaturated silane compound as a side chain is graft-copolymerized with respect to 100 parts by mass of a polyolefin resin as a main chain.
3. Item 3. The decorative material according to Item 1 or 2, wherein the decorative sheet has a synthetic resin backer layer on the back surface of the base material sheet.
4). Item 4. The cosmetic material according to any one of Items 1 to 3, wherein the total thickness of the layer containing the silane-modified polyolefin resin is 50% or more of the thickness of the decorative sheet.
5). Item 5. The cosmetic material according to any one of Items 1 to 4, wherein the colored paint contains isocyanate.

  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 is a decorative sheet in which one or two or more layers are laminated on one side or both sides of a base sheet,
(1) At least one of the layers constituting the decorative sheet contains a polyolefin resin and a silane-modified polyolefin resin,
(2) The content of the silane-modified polyolefin resin is 10% by mass or more when the total amount of the polyolefin resin and the silane-modified polyolefin resin is 100% by mass.
It is characterized by that.

  The decorative sheet according to the present invention having the above-described features is provided by coloring at least one of the layers constituting the decorative sheet by containing a specific amount of a silane-modified polyolefin resin in addition to the polyolefin resin. The adhesion is improved. Therefore, the decorative sheet of the present invention is laminated on various adherends to make a decorative material, and when a colored paint is applied to the groove portion and the chamfered portion of the decorative material, without depending on the corona treatment and the easily adhesive resin, The colored paint can be sufficiently adhered to the cross section of the decorative sheet.

  As long as the decorative sheet of the present invention satisfies the requirements (1) and (2) above, the layer structure and the resin component constituting each layer are not particularly limited. As the layer configuration, for example, a layer configuration in which one or two or more layers of a colored concealment layer, a design pattern layer, a transparent adhesive layer, a transparent resin layer, and a transparent surface protective layer are laminated on a base sheet. Can be mentioned. Moreover, you may laminate | stack the buffer layer (what is called a synthetic resin backer layer) for the purpose of the impact absorption of a decorative sheet and a decorative material, etc. on the back surface of a base material sheet. In this specification, the direction in which the transparent surface protective layer is laminated as viewed from the base sheet is referred to as “upper” or “front surface”, and the synthetic resin backer layer is viewed from the base sheet. The direction in which the layers are stacked is referred to as “lower” or “back surface”.

  In the present invention, at least one of the layers constituting the decorative sheet only needs to contain a specific amount of a silane-modified polyolefin resin in addition to the polyolefin resin. The modified resin layer ") may be any of the layers constituting the decorative sheet. For example, the modified resin layer may be any one of a base sheet, a transparent resin layer, and a synthetic resin backer layer, may be two layers, may be three layers, and may be all of the layers constituting the decorative sheet. May be.

  In the present invention, the position of the modified resin layer can be appropriately set according to the type of matrix resin constituting each layer. For example, when the transparent resin layer is a modified resin layer, the adhesion with the surface protective layer can be improved without performing corona treatment on the transparent resin layer.

  In the case where the base sheet is a modified resin layer, the adhesion to the pattern printing layer, the synthetic resin backer layer, etc. can be improved without subjecting the base sheet to corona treatment. In addition, when the base sheet is a modified resin layer and does not have a synthetic resin backer layer, primer treatment is not required on the back side of the base sheet (the surface to which the adherend is bonded). Adhesiveness with the adhesive used for adhesion of the adherend can be improved.

  When the synthetic resin backer layer is used as the modified resin layer, the adhesion with the base material sheet can be improved without performing corona treatment, primer treatment or the like on the synthetic resin backer layer. When the synthetic resin backer layer is used as the modified resin layer, the adhesive used for adhering the adherend is not required even if the primer treatment is not performed on the back surface of the synthetic resin backer layer (the surface to which the adherend is adhered). Adhesiveness with the agent can be improved.

  In the present invention, the thickness of the modified resin layer (the total thickness in the case of two or more modified resin layers) is preferably 50% or more of the thickness of the decorative sheet, and 80% or more. More preferably. If it is 50% or more of the thickness of the decorative sheet, it is sufficient for improving the adhesion of the colored paint and maintaining the appearance quality. In order to satisfy this requirement, for example, one or more of the base sheet, the transparent resin layer, and the synthetic resin backer layer are preferably modified resin layers.

The silane-modified polyolefin resin has a structure in which an unsaturated silane compound as a side chain is graft copolymerized with a polyolefin resin as a main chain. Examples of unsaturated silane compounds include vinyltrimethoxysilane (VTMO), vinyltriethoxysilane, vinyl-tris (2-methoxy-ethoxy) silane, and 3-methacryloxypropyltrimethoxysilane (MEMO; H ₂ C = C). (CH ₃ ) COO (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ ), 3-methacryloxypropyltriethoxysilane, vinyldimethylmethoxysilane and vinylmethyldibutoxysilane are preferred. However, it is not limited to these. Of these unsaturated silane compounds, silanevinyltrimethoxysilane is particularly preferable. In addition, what is necessary is just to employ | adopt the usual method of a well-known graft polymerization for the conditions in case graft-polymerizing an unsaturated silane compound to the polyolefin resin which is a principal chain.

  The type of polyolefin resin that is the main chain is not particularly limited, but is preferably the same as the type of polyolefin resin that serves as a matrix constituting the modified resin layer. The graft amount of the unsaturated silane compound is not limited, but 0.5 to 20 parts by mass of the unsaturated silane compound that is a side chain with respect to 100 parts by mass of the polyolefin resin that is the main chain is preferably graft copolymerized, More preferably, it is 0.5-10 mass parts. By modifying the polyolefin resin of the main chain within such a range of the graft amount, it becomes easy to obtain an effect of improving the adhesion with the colored paint as the modified resin layer.

In the present invention, it is considered that the reason why the adhesion of the colored paint to the cross section of the decorative sheet is improved by providing the modified resin layer is as follows. That is, the silyl group (Si (OR) ₃ ) (where R is any hydrocarbon group such as a methyl group or an ethyl group) possessed by the silane-modified polyolefin resin is a hydrolyzable group, and is in the air or in a colored paint. It is hydrolyzed by moisture to form a silanol group (Si (OH) ₃ ). And this silanol group has the following two points:
・ When a coloring agent contains a curing agent (eg, isocyanate), a chemical bond (-NH · CO · OSi _≡ ) is formed by reaction.
・ The wettability of the cross section (surface) of the modified resin layer is improved.
As a result, the adhesion of the colored paint to the cross section of the decorative sheet is improved.

  In order to obtain the former action, it is preferable to employ a paint containing a curing agent such as an isocyanate that chemically bonds to a silanol group as the colored paint.

  The higher the content of the silane-modified polyolefin in the modified resin layer, the better the adhesion of the colored paint, but the silanol group itself has crosslinkability, and if the content is high, the modified resin layer is crosslinked. The shrinkage of the increases. Therefore, if the content is large, the decorative sheet may curl or cause problems when the decorative sheet is laminated on the adherend. Therefore, the content of the silane-modified polyolefin resin is 10% by mass or more, with the total amount of the polyolefin resin and the silane-modified polyolefin resin being 100% by mass, and preferably 10 to 50% by mass.

  The modified resin layer may contain a known easy-adhesive resin or the like as another component as long as it satisfies the requirements (1) and (2) and does not impair the effects of the present invention. However, when acid-modified polypropylene is contained as an easy-adhesive resin, there is a risk of whitening during the above-described bending process, reduction in impact resistance of the synthetic resin backer layer, etc. It is preferable that it is 30 mass% or less in 100 mass% of resin components contained therein.

  Hereinafter, for each of the above-exemplified layers (base sheet, colored hiding layer, design pattern layer, transparent adhesive layer, transparent resin layer, transparent surface protective layer, and synthetic resin backer layer), (1) and Explain general contents other than the requirement (2).

(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 can be 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 combination of one 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.

(Colored hiding layer)
A colored concealment layer may be further formed between the base sheet and the pattern layer as necessary. The colored hiding layer is provided when it is desired to hide the ground color of the wooden board 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.

(Transparent adhesive layer)
A transparent adhesive layer can be formed on the pattern layer.

  The transparent adhesive layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent. The transparent adhesive layer can be formed in order to bond the pattern layer and the transparent resin layer.

  It does not specifically limit as an adhesive agent, A well-known adhesive agent can be used in the field of a decorative sheet.

  Examples of the adhesive known in the field of decorative sheets include thermoplastic resins such as polyamide resin, acrylic resin and vinyl acetate resin, and curable resins such as thermosetting urethane resin. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied.

  The adhesive layer can be formed, for example, by applying an adhesive on the pattern layer, applying a coating agent (adhesive) that constitutes the transparent resin layer, and drying and curing. Conditions such as drying temperature and drying time are not particularly limited, and may be set as appropriate according to the type of adhesive. The method of applying the adhesive is not particularly limited, and examples thereof include roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, and comma coating. The method can be adopted.

  Although the thickness of an adhesive bond layer is not specifically limited, The thickness after drying is 0.1-30 micrometers, Preferably it is about 1-20 micrometers.

(Transparent resin layer)
A transparent resin layer may be formed on the transparent adhesive layer. The transparent resin layer includes any of colorless and transparent, colored and transparent, and translucent as long as it is transparent.

  The resin component contained in the transparent resin layer is not limited, but a thermoplastic resin is preferable, among which polyolefin and polyester are preferable, and polypropylene is most preferable. It is preferable that the transparent resin layer is substantially formed of a polypropylene resin.

  The transparent resin layer is formed of, for example, polypropylene resin by a calendar method, an inflation method, a T-die extrusion method, or the like. An existing film may be used.

  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 outermost layer side 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 floor 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. Although the thickness of a backer layer is not limited, 100-600 micrometers 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.

Flooring decorative material The decorative sheet of the present invention can be made into a decorative 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. Examples of the adhesive include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, butadiene / acrylonitrile rubber, neoprene rubber, natural rubber, and the like as active ingredients. Any known adhesive can be used.

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

  The decorative material of the present invention may be provided with a groove portion and / or a chamfered portion from the decorative sheet side to the adherend, and the groove portion and the chamfered portion may be painted with a colored paint.

  As the colored paint for coating the groove and the chamfered portion, for example, an ink can be used by dissolving or dispersing a colorant that can also be used in the adhesive layer in a vehicle. Examples of the colorant are the same as described above. Vehicles include, for example, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane composed of isocyanate and polyol, polyacryl, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and cellulose series. Examples thereof include resins and polyamide resins. These vehicles can be used alone or in admixture of two or more. In addition, it is preferable to employ | adopt the thing containing hardening | curing agents, such as isocyanate which chemically couple | bonds with the silanol group of a modified resin layer as a colored coating material as above-mentioned. In addition, a solvent, an auxiliary agent, and the like can be added as necessary.

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

  The decorative material shown in FIG. 1 has a configuration in which a synthetic resin backer layer 2 and a decorative sheet 3 are laminated on an adherend 1 via a colored adhesive layer 6, and the adherend 1 from the decorative sheet 3 side. V-shaped groove part 4-1 and C chamfered part 4-2 are provided. A colored coating film 5 is formed on the surfaces of the V-shaped groove part 4-1 and the C chamfered part 4-2.

  The decorative material shown in FIG. 2 has an adhesive layer 24, a primer layer 25, a base material sheet 26, a colored hiding layer 27, a pattern layer 28, an adhesive layer 29, and a transparent resin layer on a synthetic resin backer layer 23. 30, a primer layer (not shown) and a surface protective layer 31 are laminated in order. Embossing is performed from the surface protective layer side, and a concave embossed portion 32 is provided. On the other hand, the adherend 21 is laminated on the back surface of the synthetic resin backer layer via the colored adhesive layer 22. In this decorative material, a V-shaped groove 20 reaching the adherend 21 from the decorative sheet side is provided.

  In the decorative sheet of the present invention, at least one of the layers constituting the decorative sheet contains a specific amount of a silane-modified polyolefin resin in addition to the polyolefin resin, so that the adhesion of the colored paint to the cross section of the decorative sheet is improved. It has been improved. Therefore, the decorative sheet of the present invention is laminated on various adherends to make a decorative material, and when a colored paint is applied to the groove portion and the chamfered portion of the decorative material, without depending on the corona treatment and the easily adhesive resin, The colored paint can be sufficiently adhered to the cross section of the decorative sheet.

It is a schematic diagram (an example) of the decorative material for floors of the present invention. It is a schematic diagram (an example) of the decorative material for floors 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 60 μm-thick polypropylene film (base material sheet) to which 20% by mass of a silane-modified polyolefin resin was added was prepared and subjected to corona discharge treatment on both sides. A pattern printing layer having a thickness of 2 μm was formed on one surface of the base sheet with a printing ink made of a two-component curable acrylic urethane resin. On the pattern printing layer, a urethane resin adhesive was applied so that the solid content was 3 g / m ² to form an adhesive layer. On the adhesive layer, using a T-die extruder, a polypropylene resin to which 20% by weight of a silane-modified polyolefin resin was added was heated and melt extruded to form a transparent resin layer having a thickness of 80 μm. After the corona discharge treatment is applied to the surface of the transparent resin layer, a primer layer is formed by applying acrylic urethane resin to the surface subjected to the corona discharge treatment so that the solid content is 1 g / m ² did. Apply urethane acrylate ionizing radiation curable resin to the surface of the primer layer by a roll coating method so that the solid content is 15 g / m ² , then use an electron beam irradiation device in an environment with an oxygen concentration of 200 ppm or less A surface protective layer was formed by irradiating with an electron beam under the conditions of an acceleration voltage of 125 KeV and 5 Mrad. A decorative sheet (total thickness: 160 μm) was prepared by forming an uneven pattern with a grain conduit pattern of 30 μm deep by embossing from the surface protective layer side.
(Creating cosmetics)
The produced decorative sheet was bonded to the plywood via a water-based adhesive (BA-10L / BA-11B, manufactured by Chuo Rika Kogyo Co., Ltd.), and then the edge of the decorative material was subjected to C surface processing by cutting. Finally, a cosmetic material was prepared by painting the C surface with a two-component curable water-based paint on the coating line.

Example 2
A cosmetic material was produced in the same manner as in Example 1 except that the amount of the silane-modified polyolefin added to the 60 μm polypropylene film (base sheet) was 0% by weight.

Example 3
A cosmetic material was produced in the same manner as in Example 2 except that the amount of the silane-modified polyolefin added to the transparent resin layer was 10% by weight.

Example 4
(Production of decorative sheet)
Corona discharge treatment was performed on both sides of a 60 μm-thick polypropylene film (base material sheet). A pattern printing layer having a thickness of 2 μm was formed on one surface of the base sheet with a printing ink made of a two-component curable acrylic urethane resin. On the pattern printing layer, a urethane resin adhesive was applied so that the solid content was 3 g / m ² to form an adhesive layer. On the adhesive layer, a polypropylene resin was heated and melt extruded using a T-die extruder to form a transparent resin layer having a thickness of 80 μm. After the corona discharge treatment is applied to the surface of the transparent resin layer, the primer layer is formed by applying an acrylic urethane resin to the surface subjected to the corona discharge treatment so that the solid content is 1 g / m ^2. Formed. Apply urethane acrylate ionizing radiation curable resin to the surface of the primer layer by a roll coating method so that the solid content is 15 g / m ^2, and then use an electron beam irradiation device in an environment with an oxygen concentration of 200 ppm or less. A surface protective layer was formed by irradiating and curing an electron beam under conditions of an acceleration voltage of 125 KeV and 5 Mrad. An intermediate sheet (total thickness: 160 μm) was prepared by forming an uneven pattern with a grain conduit pattern of 30 μm deep by embossing from the surface protective layer side. A synthetic resin backer layer was formed by extruding and laminating a transparent resin on the back surface of the intermediate sheet by an extrusion laminating method. The thickness of the backer layer was 250 μm, and the material was a polypropylene resin to which 10% by weight of silane-modified polyolefin was added.
(Creating cosmetics)
The produced decorative sheet was bonded to the plywood via a water-based adhesive (BA-10L / BA-11B, manufactured by Chuo Rika Kogyo Co., Ltd.), and then the edge of the decorative material was subjected to C surface processing by cutting. Finally, a cosmetic material was prepared by painting the C surface with a two-component curable water-based paint on the coating line.

Comparative Example 1
A cosmetic material was prepared in the same manner as in Example 1 except that the amount of the silane-modified polyolefin added to the base sheet and the transparent resin layer was 5% by weight, respectively.

Test Example 1 (Coating adhesion evaluation by sero resistance test)
Nichiban cellophane tape was affixed to the coated decorative material C surface and pulled strongly in the 90 ° C direction. After the sero resistance test, two points were evaluated: adhesion evaluation and appearance evaluation.

Both the results of the adhesion evaluation and the external appearance evaluation were evaluated as pass or better.
-Adhesion evaluation criteria Only the layer portion to which the silane-modified polyolefin is added is evaluated.
○: No peeling of paint Δ: The remaining area of the paint is 70% or more ×: The remaining area of the paint is less than 70%.
○: There is almost no part to which the paint is not attached, and the appearance quality is not impaired.
(Triangle | delta): The part which the coating material does not adhere is conspicuous slightly.
X: The part which the coating material does not adhere is conspicuous.

1. 1. Adhering material 2. Synthetic resin backer layer Decorative sheet 4-1. V-shaped groove 4-2. C chamfer 5. 5. Colored coating film Colored adhesive layer 20. V-shaped groove 21. Substrate 22. Colored adhesive layer 23. Synthetic resin backer layer 24. Adhesive layer 25. Primer layer 26. Base sheet 27. Colored hiding layer 28. Pattern pattern layer 29. Transparent adhesive layer 30. Transparent resin layer 31. Surface protective layer 32. Embossed part

Claims (5)

A decorative material in which a decorative sheet is laminated on an adherend via an adhesive layer,
The decorative material has a groove portion and / or a chamfered portion from the decorative sheet side to the adherend, and the groove portion and the chamfered portion are painted with a colored paint,
The decorative sheet has one or more layers laminated on one side or both sides of the base sheet ,
(1) At least one of the layers constituting the decorative sheet contains a polyolefin resin and a silane-modified polyolefin resin,
(2) The content of the silane-modified polyolefin resin is 10% by mass or more when the total amount of the polyolefin resin and the silane-modified polyolefin resin is 100% by mass.
A cosmetic material characterized by that. 2. The decorative material according to claim 1, wherein the silane-modified polyolefin resin has a structure in which 0.5 to 20 parts by mass of an unsaturated silane compound as a side chain is graft-copolymerized with respect to 100 parts by mass of a polyolefin resin as a main chain. 3. The decorative material according to claim 1 , wherein the decorative sheet has a synthetic resin backer layer on the back surface of the base sheet. 4. The decorative material according to claim 1, wherein the total thickness of the layer containing the silane-modified polyolefin resin is 50% or more of the thickness of the decorative sheet. The cosmetic material according to any one of claims 1 to 4, wherein the colored paint contains isocyanate.

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