JP5169694B2 - Decorative sheet - Google Patents

Description

The present invention relates to a decorative sheet.

  The decorative sheet is used by being attached to various adherends. At that time, a decorative sheet is known in which a colored layer (colored solid layer) is formed on a base sheet for the purpose of concealing the ground color of the adherend. The colored layer needs to be sufficiently adhered to the base sheet so as not to peel from the base sheet. In particular, decorative sheets used in exteriors such as outer walls and roofs and bathrooms have higher adhesion between the base sheet and the colored layer even when exposed to rain, tap water, etc., compared to ordinary interior decorative sheets. Is required to maintain. That is, weather resistance and water resistance are required for the adhesion between the base sheet and the colored layer (durable adhesion is required).

  Since the sheet | seat formed using polyolefin resin is often used as a base material sheet, in this case, the said colored layer needs to have durable adhesiveness with respect to a polyolefin-type base material sheet.

  Conventionally, the resin described in Patent Document 1 has been used as the resin component of the colored layer. That is, chlorinated polyolefin resins such as chlorinated polyethylene and chlorinated polypropylene, polyester resins, urethane resins, acrylic resins, polyvinyl acetate, vinyl chloride / vinyl acetate copolymers, and cellulose resins are used.

  However, when these resins are used, there is a problem that sufficient initial adhesion with the substrate sheet cannot be obtained. If the initial adhesion is not sufficient, there arises a problem (back trap) that the colored layer forming composition adheres to a printing device for printing the colored layer. In this case, it is difficult to print the colored layer continuously.

  In order to solve such a problem, it has been proposed to use polyester urethane or acrylic polyol as the resin component of the colored layer.

  However, since polyester-based urethane is easily hydrolyzed, there is a problem that the durable adhesion cannot be obtained sufficiently. Acrylic polyols also cannot provide sufficient durable adhesion. This is because when an acrylic polyol is used as a resin component, the colored layer becomes hard and brittle, and stress concentration occurs.

Therefore, development of a decorative sheet in which the colored layer has excellent durability adhesion to the polyolefin-based substrate sheet is eagerly desired.
JP2008-30493

  This invention makes it a main subject to provide the decorative sheet in which a colored layer has the durable adhesiveness excellent with respect to the polyolefin-type base material sheet.

  As a result of intensive studies, the present inventor has found that the above problem can be solved by including a specific resin as a resin component of the colored layer, and has completed the present invention.

That is, the present invention relates to the following decorative sheet.
1. A decorative sheet having a colored layer containing a polycarbonate urethane-acrylic polyol copolymer and a polyester urethane as a resin component.
2. Item 2. The item 1, wherein the colored layer contains a pigment, and the mass of the solid content of the pigment in the colored layer / the mass of the solid content of the resin component (P / V ratio) is 1 to 3. Makeup sheet.
3. Item 3. The decorative sheet according to Item 2, wherein the colored layer is formed by applying a colored ink containing the resin component and the pigment, and the coating amount is 1 to 10 g / m ² .
4). Item 4. The decorative sheet according to any one of Items 1 to 3, wherein a polyolefin-based substrate sheet and the colored layer are sequentially laminated.
5. Item 5. The decorative sheet according to Item 4, wherein the base sheet, the colored layer, the pattern layer, and the transparent surface protective layer are sequentially laminated.
6). A cosmetic material obtained by sticking the decorative sheet according to any one of Items 1 to 5 to an adherend.
7). Item 7. The cosmetic material according to Item 6, which is for exterior use or bathroom use.

  The decorative sheet of the present invention has a colored layer containing a polycarbonate-based urethane-acrylic polyol copolymer and a polyester-based urethane as resin components.

  The present invention uses a combination of a polycarbonate-based urethane-acrylic polyol copolymer and a polyester-based urethane as a resin component of a colored layer, thereby coloring a decorative sheet formed by sequentially laminating a polyolefin-based substrate sheet and a colored layer. A decorative sheet excellent in durability adhesion between the layer and the substrate sheet can be provided.

  As long as the decorative sheet of the present invention has the colored layer, the layer structure is not particularly limited. For example, the decorative sheet of the present invention includes a decorative sheet obtained by laminating an olefin-based substrate sheet, the colored layer, the pattern layer, and the transparent surface protective layer in this order.

  Hereinafter, the decorative sheet of the present invention will be specifically described with the decorative sheet having such a layer structure as a representative example.

As the base sheet, a film formed using a thermoplastic resin can be used. For example, an acrylic resin, a polyester resin (PET), a polyolefin resin, and the like are preferable, and particularly, a film formed using a polyolefin resin. Olefin base sheets are preferred.

  As said 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 plastomer, Examples thereof include polyolefin-based thermoplastic elastomers. These can be used alone or in combination of two or more. Among these, polyethylene, polypropylene, polyolefin-based thermoplastic plastomer, polyolefin-based thermoplastic elastomer and the like are particularly preferable.

  The polyolefin resin is preferably a homopolymer or a copolymer mainly composed of polypropylene. For example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and a copolymer of a crystalline part of polypropylene and an α-olefin having 2 to 20 carbon atoms other than propylene can be given. 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-based thermoplastic elastomer is a block polymer using isotactic polypropylene as a hard segment and atactic polypropylene as a soft segment. In particular, an elastomer obtained by mixing a hard segment made of isotactic polypropylene and a soft segment made of atactic polypropylene at a weight ratio of 80:20 is preferable.

  A well-known 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). These can be used alone or in combination of two or more. About the compounding quantity of the said additive, it can set suitably according to a product characteristic.

  It does not specifically limit as a coloring agent, Well-known coloring agents, such as a pigment and dye, can be used. For example, one or more of the pigments listed in the item of the colored layer below can be used.

  The base sheet is obtained by forming a resin composition containing the resin component or the like into a film by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like.

  The thickness of the base material sheet is usually about 50 to 150 μm, preferably about 60 to 80 μm.

  Corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromate treatment on the front surface and back surface of the base sheet (the surface opposite to the surface on which the following colored layers are laminated) as necessary A surface treatment such as the above may be applied. For example, when the corona discharge treatment is performed, the surface tension of the substrate sheet surface may be 35 dyne or more, preferably 40 dyne or more. The surface treatment may be performed according to a conventional method for each treatment.

  You may provide a primer layer in the back surface of a base material sheet as needed.

  A primer layer can be formed by apply | coating a well-known primer agent to the back surface of a base material sheet. As the primer agent, for example, an acrylic-urethane resin-based primer agent made of an acrylic-modified urethane resin or the like is preferable in terms of weather resistance.

The application amount of the primer agent is usually about 0.1 to 10 g / m ² , preferably about 0.1 to 5 g / m ² .

  The thickness of the primer layer is usually about 0.01 to 10 μm, preferably about 0.1 to 5 μm.

Colored layer The decorative sheet of the present invention has a colored layer formed using a polycarbonate urethane-acrylic polyol copolymer and a polyester urethane as resin components.

  The copolymerization ratio of the polycarbonate urethane and the acrylic polyol in the polycarbonate urethane-acrylic polyol copolymer is not limited, and may be appropriately set within a range that can sufficiently maintain the durable adhesion between the base sheet and the colored layer. That's fine.

  The polymerization form of each structural unit (polycarbonate urethane and acrylic polyol) in the copolymer is not particularly limited, and may be any of alternating polymerization, block polymerization, random polymerization, and the like.

  Polyester urethane is obtained by, for example, reacting a polyester polyol and a diisocyanate compound.

  The content of the polyester urethane in the colored layer is preferably about 10 to 100 parts by weight, more preferably about 20 to 70 parts by weight with respect to 100 parts by weight of the polycarbonate urethane-acrylic polyol copolymer.

  The content ratio of the polycarbonate-based urethane-acrylic polyol copolymer and the polyester-based urethane in the colored layer (the polycarbonate-based urethane-acrylic polyol copolymer / the polyester-based urethane) is 50/50 to 90 by weight. / 10 is preferable, and about 60/40 to 80/20 is more preferable. In particular, when the content ratio (the polycarbonate-based urethane-acrylic polyol copolymer / the polyester-based urethane) is about 60/40 to 80/20 by weight ratio, the initial adhesion and durable adhesion of the colored layer to the base material sheet Sex is effectively expressed.

  The colored layer preferably further contains a pigment. By containing the pigment, the design of the decorative sheet can be improved, and the ground color of the adherend (base) can be concealed from the front surface of the decorative sheet.

  Examples of the pigment 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 pigments can be used singly or in combination of two or more.

  Although the content of the pigment in the colored layer is not particularly limited, an amount in which the mass of the solid content of the pigment / the mass of the solid content of the resin component (P / V ratio) is 1 to 3 is preferable. An amount of 0.5 is more preferred, and an amount of 1 is most preferred. In particular, when the P / V ratio is 1 to 1.5, the colored layer becomes flexible, so that adhesion to the substrate sheet (particularly, adhesion with excellent water resistance) can be suitably imparted to the colored layer. Further, the durability adhesion is improved.

  The colored layer may further contain a known additive generally used as a material for the colored layer, if necessary. Examples of known additives include fillers such as silica, extender pigments such as calcium carbonate, neutralizers, and surfactants.

  The method for forming the colored layer is not particularly limited. For example, the whole base sheet is covered with a colored ink obtained by dissolving (or dispersing) the raw material together with the resin component in a solvent (or dispersion medium). It is formed so as to be (solid on the entire surface).

  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, 2-methoxyethyl acetate, and 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 Inorganic solvents and the like, such as water; chlorinated organic solvents. These solvents (or dispersion media) can be used alone or in admixture of two or more.

  Preferred examples of the color ink coating method include 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, and dip coating method described above. As mentioned.

The coating amount of the coloring ink is preferably about 1 to 10 g / ^{m 2,} about 4-6 g / ^{m 2} is more preferable. The coating amount is desirably adjusted according to the P / V ratio of the colored layer (colored ink) to be formed. For example, when the P / V ratio of the colored layer is 3 and the coating amount is about 1 to 3 g / m ^{2, the} concealability of the colored layer can be secured, but the colored layer is hard and brittle. There is a risk that the durable adhesion between the base material sheet and the substrate sheet becomes insufficient. In this case, this problem can be suitably avoided by setting the coating amount to about 4 g / m ² or more. When the P / V ratio of the colored layer is 1 to 1.5, the concealability of the colored layer may be insufficient when the coating amount is about 1 g / m ² . If the concealability of the colored layer is insufficient, there is a problem that ultraviolet rays reach the interface between the base sheet and the colored layer, resulting in a decrease in adhesion. In this case, this problem can be suitably avoided by setting the coating amount to about 4 g / m ² or more.

Picture layer A picture layer is formed on the colored layer (front surface).

  The pattern layer imparts design properties with a desired pattern to the decorative sheet, and the type of the pattern is not 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.

  In addition, as shown in FIG. 1 below, a pattern layer formed on a colored layer may be referred to as a pattern pattern layer.

  Although the formation method of a pattern layer is not specifically limited, It is preferable to print on the said colored layer using the said colored ink.

  Examples of the printing method include a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an ink jet printing method.

  The thickness of the pattern layer can be appropriately set according to product characteristics, but the layer thickness at the time of coating is usually about 1 to 15 μm, and the layer thickness after drying is about 0.1 to 10 μm.

Transparent adhesive layer A transparent adhesive layer may be formed on the pattern layer as necessary. The transparent adhesive layer is not particularly limited as long as it is transparent, and includes any of transparent and colorless, colored and translucent. This adhesive layer is 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 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. These can be used alone or in combination of two or more.

  As a method for forming a transparent adhesive layer, for example, an adhesive is applied on the following transparent resin layer, dried and cured to form a transparent adhesive layer, and then the obtained laminate is used as the laminate. The method of laminating | stacking on the said pattern layer by the dry laminating method is mentioned so that a pattern layer and this transparent adhesive layer may contact | connect.

  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. 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 dry laminating method may follow a known method.

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

Transparent resin layer A transparent resin layer may be formed on the picture layer (or the transparent adhesive layer) as necessary. The transparent resin layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent, and translucent.

  Examples of the resin component forming the transparent resin layer include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-acrylic. Examples include acid ester copolymers, ionomers, polymethylpentene, acrylic acid esters, methacrylic acid esters, polycarbonates, and cellulose triacetates. Among the above, polyolefin resins such as polypropylene are preferable. More preferably, it is a polyolefin resin having stereoregularity. When using a polyolefin resin, it is desirable to form a transparent resin layer by extruding 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 Various additives such as rubber (for example, rubber) may be included.

  As a method for forming a transparent resin layer, a resin composition containing the above resin component or the like is laminated on a pattern layer (or a transparent adhesive layer) by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like. A method is mentioned.

  The thickness of the transparent resin layer is not particularly limited, but is generally about 10 to 150 μm.

  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.

  Moreover, you may provide the primer layer (The primer layer for making formation of a transparent surface protective layer easy) on the surface as needed.

  The primer layer can be formed by applying a known primer agent to the surface of the transparent resin layer. As the primer agent, those exemplified above can be used.

The application amount of the primer agent is not particularly limited, but is usually 0.1 to 100 g / m ² , preferably about 0.1 to 50 g / m ² .

  Although the thickness of a primer layer is not specifically limited, Usually, 0.01-10 micrometers, Preferably it is about 0.1-1 micrometer.

Transparent surface protective layer A transparent surface protective layer is formed on the pattern layer (transparent adhesive layer or transparent resin layer).

  Examples of the surface protective layer include a surface protective layer made of an ionizing radiation curable resin. By forming a surface protective layer made of an ionizing radiation curable resin, the abrasion resistance, impact resistance, stain resistance, scratch resistance, weather resistance, etc. of the decorative sheet can be improved.

  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.

  In particular, as the ionizing radiation curable resin, a prepolymer having a radical polymerizable unsaturated group is preferable, and urethane acrylate is more preferable.

  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 them, those capable of irradiating electrons having energy of 100 to 1000 keV, preferably 100 to 300 keV are preferable.

  The transparent surface protective layer is formed by, for example, applying an ionizing radiation curable resin on the transparent resin layer (or the primer layer) by a known coating method such as gravure coating or roll coating, and then irradiating with ionizing radiation. It can be formed by curing the resin.

  The transparent surface protective layer may further contain a known additive as required. Examples of the additive include an ultraviolet absorber, the light stabilizer, a filler, a matting agent, a flame retardant, a lubricant, and an antioxidant.

  The thickness of the transparent 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 An embossed pattern may be applied to the front surface of the decorative sheet of the present invention as necessary. The embossed pattern can be applied by, for example, a known embossing roll. For example, a desired embossed pattern can be formed by pressing from 100 to 180 ° C. from the transparent surface protective layer side using an embossing roll. Embossed patterns include wood grain plate conduit grooves, stone plate surface irregularities, cloth surface textures, satin texture, sand texture, hair lines, and multi-line grooves.

Cosmetic Material The cosmetic material of the present invention is obtained by adhering the decorative sheet to an adherend. The decorative material of the present invention can be suitably used even in an environment exposed to rain, tap water, etc., because the colored layer of the laminated decorative sheet has excellent durability adhesion to the polyolefin-based substrate sheet. . For example, it is suitably used for exteriors such as outer walls and roofs and bathrooms.

  The adherend is not limited, and the same materials as known decorative sheets can be used. For example, a wood material, a metal, ceramics, plastics, glass, etc. are mentioned. In particular, the decorative sheet of the present invention can be suitably used for a wood material. Specifically, wood materials include veneer, wood veneer, wood plywood, particle board, medium density fiberboard (MDF) made from various materials such as cedar, firewood, firewood, pine, lawan, teak, and melapie. ) And the like.

  The lamination method is not limited. For example, a method of sticking a decorative sheet to an adherend with an adhesive or the like can be employed. What is necessary is just to select an adhesive agent suitably from well-known adhesive agents according to the kind etc. of to-be-adhered material. Examples thereof 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. These adhesives are used alone or in combination of two or more.

  In the decorative sheet of the present invention, the colored layer has excellent durability adhesion to the polyolefin-based substrate sheet. That is, the adhesion force excellent in weather resistance and water resistance is exhibited between the base sheet and the colored layer. Therefore, the decorative material using the decorative sheet of the present invention is suitably used for exteriors such as outer walls and roofs, bathrooms, and the like.

  In addition, the decorative sheet of the present invention is excellent in initial adhesion between the colored layer and the base sheet. Therefore, the back trap at the time of forming a colored layer can be avoided suitably.

  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
A decorative sheet having the structure shown in FIG. 1 was produced by the following method.

As the substrate 2, a resin sheet (trade name “PB-010” manufactured by Mitsubishi Plastics) made of colored polypropylene resin (thickness: 80 μm) was prepared. After the front surface and the back surface were subjected to corona discharge treatment, a colored layer 3b was formed on the surface. The colored layer 3b was formed in a solid form on the entire surface of the base material 2 using a colored ink (P / V ratio = 1) in which the resin components, pigments, and the like shown in Table 1 below were blended in the proportions shown in Table 1. Application amount: 1 g / m ² ).

  A woodgrain pattern layer 3a was formed by gravure printing the colored ink on the colored layer 3b.

  On the other hand, a back primer layer 8 (thickness 2 μm) using urethane resin as a binder was formed on the back surface by gravure printing.

  Polypropylene resin is heated and melt extruded with a T-die extruder to form a transparent resin layer 5 having a thickness of 80 μm, and a coating liquid made of a two-component curable urethane resin is coated on the transparent resin layer 5 to be transparent. The adhesive layer 4 (thickness 15 μm in a dry state) was formed, and the adhesive layer side was laminated on the pattern layer 3a by a dry laminating method.

  Next, the primer layer 6 was formed on the transparent resin layer 5. First, urethane acrylic with a urethane component to acrylic component mass ratio of 7/3 as a binder, trade name “Tinuvin 400” (manufactured by Ciba Specialty Chemicals) as a UV absorber, trade name “hindered amine light stabilizer” A resin composition containing 2% by mass of Tinuvin 123 ”(manufactured by Ciba Specialty Chemicals) was prepared.

This resin composition and hexanemethylene diisocyanate (curing agent) were mixed at a mass ratio of 100: 5, and the mixture was applied onto the transparent resin layer 5 to form a primer layer 6. The application amount of the mixture was 2.5 g / m ² . The thickness of the primer layer 6 was about 2 μm.

On the primer layer 6, an ionizing radiation polymerizable oligomer composed of 80% by weight of the bifunctional urethane acrylate oligomer (A) and 20% by weight of the hexafunctional urethane acrylate oligomer (B) has a solid content of 5 g / m ² by roll coating. Coating and drying were performed to form an uncured electron beam curable resin layer.

  The bifunctional urethane acrylate oligomer is formed by bonding a) isophorone diisocyanate, b) polyester diol (condensation product of adipic acid and ethylene glycol) and c) 2-hydroxyethyl acrylate, and has a weight average. The molecular weight is 1700.

  As the hexafunctional urethane acrylate oligomer, product name “UA306H” manufactured by Kyoeisha Chemical Co., Ltd. was used.

  After forming an uncured electron beam curable resin layer, in an environment with an oxygen concentration of 200 ppm, the uncured resin layer is irradiated with an electron beam under conditions of an acceleration voltage of 125 KeV and 5 Mrad to cure the resin to obtain a 15 μm thick electron. A line curable resin layer (transparent surface protective layer 7) was formed.

  A decorative sheet was prepared by the above process.

Example 2
A decorative sheet was prepared in the same manner as in Example 1 except that the amount of the colored ink applied was 3 g / m ² .

Example 3
A decorative sheet was prepared in the same manner as in Example 1 except that the amount of the colored ink applied was 6 g / m ² .

Example 4
A decorative sheet was produced in the same manner as in Example 1 except that the amount of the colored ink applied was 10 g / m ² .

Example 5
Example 3 except that the content ratio of the polycarbonate-based urethane-acrylic polyol copolymer and the polyester-based urethane (the polycarbonate-based urethane-acrylic polyol copolymer / the polyester-based urethane) was set to 70/30 by weight. A decorative sheet was prepared in the same manner.

Example 6
Example 3 except that the content ratio of the polycarbonate urethane-acrylic polyol copolymer and the polyester urethane (the polycarbonate urethane-acrylic polyol copolymer / the polyester urethane) was 60/40 by weight ratio. A decorative sheet was prepared in the same manner.

Example 7
A colored sheet 3b was formed in the same manner as in Example 3 except that a colored ink in which the blending ratio of the resin component and the pigment was changed so that the P / V ratio of the colored ink was 2, and a decorative sheet was produced. .

Comparative Example 1
A decorative sheet was prepared in the same manner as in Example 3 except that 20 parts by weight of the polycarbonate-based urethane-acrylic polyol copolymer was used without using the polyester-based urethane.

Comparative Example 2
A decorative sheet was prepared in the same manner as in Example 3 except that polycarbonate urethane was used instead of polyester urethane.

Comparative Example 3
A decorative sheet was prepared in the same manner as in Example 3 except that 20 parts by weight of polyester urethane was used without using the polycarbonate urethane-acrylic polyol copolymer.

Comparative Example 4
A decorative sheet was prepared in the same manner as in Example 3 except that 20 parts by weight of polyester urethane and acrylic polyol were used instead of the polycarbonate urethane-acrylic polyol copolymer and polyester urethane.

Comparative Example 5
A decorative sheet was prepared in the same manner as in Example 3 except that 20 parts by weight of the polycarbonate-based urethane was used without using the polycarbonate-based urethane-acrylic polyol copolymer and the polyester-based urethane.

Comparative Example 6
A decorative sheet was prepared in the same manner as in Example 3 except that 14 parts by weight of the polycarbonate-based urethane and 6 parts by weight of the acrylic polyol were used instead of the polycarbonate-based urethane-acrylic polyol copolymer and the polyester-based urethane. did.

<Durable adhesion>
1. Water resistance In Examples 1 to 7 and Comparative Examples 1 to 6, prior to forming the primer layer 6, the obtained laminate (base material 2, pattern layer 3, transparent adhesive layer 4 and transparency) A water resistance test was conducted on a laminate in which the resin layers 5 were sequentially laminated. Specifically, after the transparent adhesive layer 3 in the laminate was sufficiently dried, it was cut so that the width in the short side direction was 25.4 mm. Thereafter, a part of the resin sheet constituting the laminate (a base material 2 and a transparent resin layer 5) was peeled off to prepare a T-shaped test piece.

  The obtained test piece was immersed in warm water at 80 ° C. for 2 weeks and then dried for 3 to 5 days.

The peel strength of the test specimen after drying was measured at a peel speed of 100 mm / min in accordance with JIS K6854-3 “T-type peel”. The peel strength between the substrate 2 and the transparent resin layer 5 was 1.5 kgf. / A value exceeding 25.4 mm was evaluated as ◯, a value of 1.0 to 1.5 kgf / 25.4 mm was evaluated as Δ, and a value of less than 1.0 kgf / 25.4 mm was evaluated as ×. In addition, it seems that the decorative sheet of evaluation (circle) and (triangle | delta) can be practically used for exterior use or bathroom use.

  The results are shown in Table 2.

2. Weather resistance The laminates obtained after printing the pattern layer 3a in Examples 1 to 7 and Comparative Examples 1 to 6 (without forming the transparent adhesive layer 4 and the transparent resin layer 5) were subjected to a weather resistance test. I finished. The method of the weather resistance test is as follows.

  First, a UV lamp (trade name “M04-L21WB / SUV” manufactured by Iwasaki Electric Co., Ltd.), a lamp jacket (trade name “WJ50-SUV” manufactured by Iwasaki Electric Co., Ltd.) and an illuminance meter (trade name “UVD-365PD” manufactured by Iwasaki Electric Co., Ltd.) are provided. In addition, the laminates of Examples 1 to 7 and Comparative Examples 1 to 6 were placed in a super accelerated weathering test apparatus (trade name “I Super UV Tester SUV-W131” manufactured by Iwasaki Electric Co., Ltd.).

  The appearance of the laminate after the test and the adhesion between the substrate 2 and the colored layer 3b were evaluated as follows.

1) Appearance The appearance of the laminate after the test was visually observed.

  No change in the appearance and the original design is maintained as ◯, while the appearance is slightly changed, the original design is maintained as △, the appearance is remarkably lost and the original design is lost What was present was evaluated as x. In addition, it seems that the decorative sheet of evaluation (circle) and (triangle | delta) can be practically used for exterior use or bathroom use.

2) Adhesiveness Cellotape (registered trademark) was stuck on the printed layer 3a of the laminate after the test and peeled off. The colored layer 3b does not peel and the original design property can be maintained as ◯, the colored layer 3b is slightly peeled off, but it does not lose the original design property, and the colored layer 3b is peeled off. Remarkably, those that lost the original design were evaluated as x. In addition, it seems that the decorative sheet of evaluation (circle) and (triangle | delta) can be practically used for exterior use or bathroom use.

  The results are shown in Table 2.

It is a schematic diagram which shows the cross section of the decorative sheet produced in Examples 1-7 and Comparative Examples 1-6.

Explanation of symbols

1. Cosmetic sheet
2.Base material
3. Pattern pattern layer
3a. Pattern layer
3b. Colored layer
4.Transparent adhesive layer
5.Transparent resin layer
6.Primer layer
7.Transparent surface protective layer
8.Backside primer layer

Claims (7)

A decorative sheet having a colored layer containing a polycarbonate urethane-acrylic polyol copolymer and a polyester urethane as a resin component. The said colored layer contains a pigment, and the mass of the solid content of the pigment in the colored layer / the mass of the solid content of the resin component (P / V ratio) is 1 to 3. Makeup sheet. The decorative sheet according to claim ² , wherein the colored layer is formed by applying a colored ink containing the resin component and the pigment, and the coating amount is 1 to 10 g / m2. The decorative sheet according to any one of claims 1 to 3, wherein a polyolefin-based substrate sheet and the colored layer are sequentially laminated. The decorative sheet according to claim 4, wherein the base sheet, the colored layer, the pattern layer, and the transparent surface protective layer are laminated in this order. A decorative material obtained by adhering the decorative sheet according to any one of claims 1 to 5 to an adherend. The cosmetic material according to claim 6, which is used for exterior or bathroom.

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