JP5429129B2 - A decorative sheet for flooring that is excellent in impact resistance and scratch resistance - Google Patents

A decorative sheet for flooring that is excellent in impact resistance and scratch resistance Download PDF

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JP5429129B2
JP5429129B2 JP2010227103A JP2010227103A JP5429129B2 JP 5429129 B2 JP5429129 B2 JP 5429129B2 JP 2010227103 A JP2010227103 A JP 2010227103A JP 2010227103 A JP2010227103 A JP 2010227103A JP 5429129 B2 JP5429129 B2 JP 5429129B2
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flooring
resin
transparent
decorative sheet
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JP2011058355A (en
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康宏 松川
洋史 増田
寛章 中山
賢 木村
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大日本印刷株式会社
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Description

  The present invention relates to a decorative sheet for flooring excellent in impact resistance and scratch resistance.

  Conventionally, a polyvinyl chloride resin sheet is frequently used as a constituent material of a decorative sheet for resin flooring. In the case of using a polyvinyl chloride resin sheet, there is an advantage that the sheet hardness (hard to soft) can be easily adjusted by adjusting the addition amount of the plasticizer, and embossing can be easily performed.

  However, since polyvinyl chloride resin may release harmful graphite, chlorine-based gas, and the like during incineration, in recent years, a polyolefin-based resin that does not release chlorine-based gas or the like is used instead of polyvinyl chloride resin. It has become like this.

  As a decorative sheet for flooring using a polyolefin resin, for example, in Patent Documents 1 and 2, a printing sheet in which a printing pattern layer and a primer layer are sequentially formed on one side is laminated on a backer layer made of a polyolefin resin. Further, a decorative sheet for flooring is disclosed in which a clear sheet made of an ionomer resin is laminated on a printed sheet, and three layers made of a backer layer / printed sheet / clear sheet are laminated at the same time. Such a decorative sheet for flooring is made into a decorative material for flooring by sticking the backer layer side to various adherends. In addition, a backer layer is a reinforcement layer provided in order to provide hardness, intensity | strength, etc. to the decorative sheet for flooring.

  A decorative sheet for flooring having a backer layer easily exhibits predetermined hardness, strength, etc., and exhibits excellent impact resistance.

  However, the decorative sheet for flooring having a backer layer requires a step of bonding the backer layer portion to other portions (for example, a printing sheet) in the production process, and there is a problem that product loss is likely to occur in the step. is there.

  Therefore, it is desired to develop a decorative sheet for flooring that has a predetermined hardness, strength, etc. and exhibits excellent impact resistance without forming a backer layer.

  At present, in addition to excellent impact resistance, there is also a demand for higher scratch resistance (scratch resistance). In conventional veneer flooring, scratches, dents, etc. caused by sag processing, grooving, etc. can be almost eliminated by sanding (polishing), but a floor made by adhering a decorative sheet to the substrate. This is because the material cannot be sanded, and scratches on the surface (design surface) due to processing or the like become scratches on the final product.

JP-A-8-13740 JP-A-8-1883

  The main object of the present invention is to provide a decorative sheet for flooring that exhibits excellent impact resistance without forming a backer layer and also exhibits excellent scratch resistance.

As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by forming a specific polypropylene resin layer and a surface protective layer, and have completed the present invention.

That is, the present invention relates to the following decorative sheet for flooring excellent in impact resistance and scratch resistance and the decorative flooring using the decorative sheet.
1. On the base sheet made of polyolefin resin, there is a pattern layer, a transparent adhesive layer, a transparent polypropylene resin layer, and a transparent surface protective layer made of ionizing radiation curable resin or two-component curable urethane resin. It is a decorative sheet for flooring formed in order,
(1) The thickness of the transparent polypropylene resin layer is 150 μm or more,
(2) The universal hardness of the transparent polypropylene-based resin layer is 35 N / mm 2 or more, and (3) the universal hardness of the transparent surface protective layer is 100 N / mm 2 or more. .
2. On the base sheet made of polyolefin resin, there is a pattern layer, a transparent adhesive layer, a transparent polypropylene resin layer, and a transparent surface protective layer made of ionizing radiation curable resin or two-component curable urethane resin. It is a decorative sheet for flooring formed in order,
(I) The transparent polypropylene resin layer is composed of two layers, an upper polypropylene layer and a lower polypropylene layer,
(B) The upper polypropylene layer has a thickness of 100 μm or more,
(C) The universal hardness of the upper polypropylene layer is 35 N / mm 2 or more,
(D) The thickness of the lower polypropylene layer is 50 μm or more,
(E) The universal hardness of the lower polypropylene layer is 20 N / mm 2 or less,
(F) A decorative sheet for flooring, wherein the transparent surface protective layer has a universal hardness of 100 N / mm 2 or more.
3. Item 3. The decorative sheet for flooring according to Item 2, wherein the upper polypropylene layer has a thickness of 100 to 300 µm.
4). Item 4. The decorative sheet for flooring according to any one of Items 1 to 3, wherein a colored concealing layer is further formed between the base sheet and the pattern layer.
5. Item 5. The decorative sheet for flooring according to any one of Items 1 to 4, wherein irregularities are formed on the front surface of the transparent surface protective layer.
6). 6. A flooring decorative material obtained by sticking the base sheet side of the decorative sheet for flooring according to any one of Items 1 to 5 to an adherend.

  Hereinafter, the decorative sheet for flooring and the decorative material for flooring of the present invention will be described in detail.

The decorative sheet for flooring The decorative sheet for flooring of the present invention is a pattern sheet, a transparent adhesive layer, a transparent polypropylene resin layer, and an ionizing radiation curable resin on a base sheet made of a polyolefin resin. A decorative sheet for flooring in which a transparent surface protective layer made of a two-component curable urethane-based resin is sequentially formed,
(1) The thickness of the transparent polypropylene resin layer is 150 μm or more,
(2) The universal hardness of the transparent polypropylene-based resin layer is 35 N / mm 2 or more, and (3) the universal hardness of the transparent surface protective layer is 100 N / mm 2 or more.
(Substrate sheet)
As the base sheet, a sheet made of polyolefin resin is used. Usually, a film made of polyolefin resin may be used.

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. Among these, polypropylene, polyolefin-based thermoplastic elastomers and the like are particularly preferable.

  A homopolymer or a copolymer mainly composed of polypropylene is also preferable, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and a polypropylene crystal part, and an α-olefin having 2 to 20 carbon atoms other than propylene. Is mentioned. 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 a highly crystalline and high melting point aromatic polyester for a hard segment and an amorphous polyether having a glass transition temperature of −70 ° C. or less for a soft segment. In particular, a mixture of a hard segment made of isotactic polypropylene and a soft segment made of atactic polypropylene at a weight ratio of 80:20 is preferable.

  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 base sheet is not particularly limited and can be set according to the product characteristics, but is usually 40 to 150 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, inorganic pigments such as titanium white, zinc white, petal, vermilion, ultramarine blue, cobalt blue, titanium yellow, yellow lead, carbon black; 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 adherend (base material to which the decorative sheet is bonded) is concealed, opaque coloring may be selected. On the other hand, in order to make the ground pattern of the adherend 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 the corona discharge treatment is performed, 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 side or both sides of the base sheet, a primer layer (for example, a back surface primer layer for facilitating adhesion of the adherend, a primer layer for facilitating the formation of the pattern layer) is provided as necessary. It may be provided. By providing the primer layer, interlayer adhesion with an adjacent layer (for example, an adherend) can be increased.

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 application amount of the primer agent is not particularly limited, it 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.
(Pattern pattern layer)
A pattern layer is formed on the base sheet (opposite to the adherend attachment surface, hereinafter the same side in each layer).

  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 etc.

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

Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 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 system organic solvent; diethyl ether, dioxane, ether organic solvent such as tetrahydrofuran: dichloromethane, carbon tetrachloride, trichlorethylene, tetrachlorethylene, 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 masking layer is provided when it is desired to mask the ground color of the adherend from the front surface of the decorative sheet. Of course, when the base sheet is transparent, even when the base sheet is concealed, it may be formed to stabilize the concealment.

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

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

The thickness of the colored concealing layer is not particularly limited and can be set as appropriate according to the product characteristics. The layer thickness during 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 is formed on the pattern layer. 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 to bond the pattern layer and the transparent polypropylene 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 is, for example, coated with a transparent polypropylene resin that constitutes a transparent polypropylene resin layer (an upper polypropylene layer or a lower polypropylene layer, which will be described later), after the adhesive is applied on the pattern layer, and then dried. -It can be formed by 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 polypropylene resin layer)
A transparent polypropylene-based resin layer (single layer) is formed on the transparent adhesive layer. The transparent polypropylene resin layer has a thickness of 150 μm or more and a universal hardness of 3
5 N / mm 2 or more. By forming such a transparent polypropylene resin layer, it is possible to impart high load region scratch resistance to the decorative sheet for flooring.

Here, high scratch resistance in the high load region means that scratches, indentations, etc. are unlikely to occur when the decorative sheet surface is scratched with a high load (meaning a large load per unit area). The degree of scratch resistance in the high load region is, for example, a pencil hardness test (JIS
K 5600-5-4), Clemens test and the like.

  The universal hardness in this specification is a hardness measured using a Fischer scope H100V (manufactured by Fischer Instruments Co., Ltd.) useful for measuring the hardness of thin film coatings, elastic materials and the like. The hardness measurement performed by the Fisherscope H100V is a so-called ultra micro Vickers hardness test method. Specifically, it is a method in which the indentation depth is directly read and the sample hardness is measured in a state where a load is applied by pushing the indenter into the sample surface (for example, a transparent polypropylene resin layer). The measured value (universal hardness) is defined as follows (reference: ISO technical report). A diamond indenter (φ0.4 mm ball indenter) is used as the indenter, and the indentation depth under the test load is measured. Universal hardness is expressed as a ratio of the test load divided by the surface area of the indentation produced by the test load.

Universal hardness (N / mm 2 ) = F / S
F: Test load (N)
S: Surface area (mm 2 ) of ball indenter (φ0.4 mm) under test load
The thickness of the transparent polypropylene-based resin layer may be 150 μm or more, preferably 300 μm or more, and more preferably 400 μm or more.

Universal hardness transparent polypropylene resin layer may be at 35N / mm 2 or more but, 40N / mm 2 or more.

  For the transparent polypropylene-based resin layer, the transparent polypropylene-based resin may be laminated on the transparent adhesive layer by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like, or an existing film is used. Also good.

  The transparent polypropylene resin layer is a single layer (one layer) in the above, but may be a multilayer (two or more layers) as necessary. For example, the transparent polypropylene-based resin layer has a two-layer configuration of an upper polypropylene layer and a lower polypropylene layer, which will be described later, so that the decorative sheet for flooring has a high load area scratch resistance and a low load area scratch resistance described later. Both can be granted.

  Hereinafter, a case where the transparent polypropylene resin layer has a two-layer structure will be described.

A. Upper polypropylene layer The upper polypropylene layer is formed in order to obtain particularly high load region scratch resistance among scratch resistance.

  The thickness of the upper polypropylene layer may be 100 μm or more, preferably about 100 to 300 μm, particularly preferably about 250 μm.

Universal hardness of the upper polypropylene layer as long 35N / mm 2 or more, 40N / mm 2 or more.

B. Lower Polypropylene Layer The lower polypropylene layer is formed in order to obtain particularly low load region scratch resistance among scratch resistance. Here, high scratch resistance in the low load region means that scratches, indentations, etc. are unlikely to occur when the decorative sheet surface is scratched with a low load (meaning that the load per unit area is small). The degree of scratch resistance in the low load region can be evaluated by, for example, the Hoffman scratch test.

  The method for forming the lower polypropylene layer may be the same as the method for forming the transparent polypropylene resin layer described above. If necessary, the upper stage and the lower stage may be formed by coextrusion.

  The thickness of the lower polypropylene layer may be 50 μm or more, but is preferably 100 μm or more. The upper limit of the lower polypropylene layer is not limited, but is about 200 μm.

The universal hardness of the lower polypropylene layer may be 20 N / mm 2 or less, but is preferably 15 N / mm 2 or less.

  By forming such a lower polypropylene layer in addition to the upper polypropylene layer, a low load area scratch property can be imparted to the decorative sheet for flooring.

  The surface of the upper polypropylene layer, on which the transparent surface protective layer described later is formed, is optionally treated with a surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromate treatment, etc. May be applied. The surface treatment may be performed according to a conventional method for each treatment.

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

  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 application amount of the primer agent is not particularly limited, it 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)
On the transparent polypropylene resin layer, a transparent surface protective layer made of an ionizing radiation curable resin or a two-component curable urethane resin is formed. By forming a surface protective layer made of an ionizing radiation curable resin or a two-component curable urethane 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.

  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 two-component curable urethane resin is not particularly limited. 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) which is a curing agent component. Isocyanate, hexamethylene diisocyanate, metaxylene diisocyanate and the like) can be used.

  These surface protective layers may contain a plasticizer, a stabilizer, a filler, a dispersant, a colorant such as a dye or a pigment, a solvent, or the like, if necessary.

The surface protective layer is formed by, for example, 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 curing the resin. Can be formed. 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.

The surface protective layer may have a hardness of the above-mentioned universal hardness of 100 N / mm 2 or more, preferably 150 N / mm 2 or more. If the universal hardness of the surface protective layer is less than 100 N / mm 2 , sufficient scratch resistance may not be exhibited. The universal hardness of the entire decorative sheet formed up to the surface protective layer is preferably 45 N / mm 2 or more, and more preferably 50 N / mm 2 or more.

  Irregularities may be formed on the front surface (surface exposed to the atmosphere) of the surface protective layer. Usually, an uneven pattern is formed by embossing. The embossing method is not particularly limited. For example, a preferable method is to heat soften the front surface of the transparent acrylic resin layer, pressurize and shape with an embossing plate, and then cool. 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.

Flooring decorative material The flooring decorative sheet of the present invention can be made into a flooring 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 wood system, for example, a single board, plywood, particle board, fiber board, laminated timber and the like made of cedar, straw, firewood, lauan, 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, cutting, use of a tenor, sag processing, provision of V-shaped grooves, chamfering on four sides, etc. may be performed.

  The decorative sheet for flooring of the present invention exhibits excellent impact resistance without forming a backer layer, and also exhibits excellent scratch resistance.

  Moreover, since it is not necessary to form a backer layer, the manufacturing process of the decorative sheet for flooring can be facilitated, and the manufacturing loss that has conventionally occurred in the backer layer forming process can be eliminated.

3 is a schematic diagram of a floor decorative material produced in Experimental Example 1. FIG. It is a schematic diagram of the floor decorative material produced in Experimental Example 3.

  Experimental examples will be shown below to describe the present invention more specifically.

Experimental example 1
(Preparation of decorative sheet for flooring)
A 0.06 mm thick colored polypropylene film (base material sheet) was printed to form a pattern layer.

  Next, a transparent polypropylene-based resin layer having a thickness of 0.3 mm (300 μm) was formed by adhering a transparent polypropylene-based resin film with a urethane-based dry laminating adhesive.

Next, an electron beam curable transparent surface protective layer (15 μm) having a universal hardness of 170 N / mm 2 was formed on the transparent polypropylene resin layer.

Subsequently, embossing was given from the transparent surface protective layer side, and the decorative sheet for flooring was produced. (Preparation of decorative materials for floors)
A 12 mm lauan plywood was attached to the base sheet side of the decorative sheet for flooring to produce a decorative material for flooring. For the sticking, urethane-modified ethylene / vinyl acetate emulsion adhesive (100 g / m 2 wet) was used.
(Scratch resistance of flooring cosmetics)
The scratch resistance of the produced floor decorative material was evaluated. The following pencil hardness test and clemens test evaluate the high load region scratch resistance. The Hoffman scratch test evaluates scratch resistance in the low load region. Each test method is as follows.

1. Pencil hardness test (high load evaluation)
The test was conducted with a pencil hardness tester. The test was conducted in accordance with JIS K 5600-5-4 except that the test machine was set so that the tip of the pencil applied a load of 1000 g to the decorative sheet when the test machine was in the horizontal position.

2. Hoffman scratch test (low load evaluation)
The test was conducted using a Hoffman scratch tester manufactured by BYK-GARDNER, USA. Specifically, a scratch blade (φ7 cylindrical blade) was set so as to be in contact with the decorative material surface at an angle of 45 °, and the tester was moved on the decorative material. The load (weight) was gradually increased, and the test was repeated until scratches, indentations and the like were generated on the surface of the decorative material.

3. Clemens test (high load evaluation)
The test was conducted according to JIS K 5600-5-5. As a needle for scratching the surface of the decorative material, a diamond needle was used.

  The test results are shown in Table 1 below.

HU: Universal hardness (N / mm 2 ) PP: Polypropylene * 1: Hardness at which neither whitening scratches nor dent scratches occur * 2: Maximum load at which whitening scratches do not occur (g)
* 3: Maximum load at which no whitening damage occurs (g) These units are the same as below.

Experimental example 2
A flooring decorative material was prepared in the same manner as in Experimental Example 1, except that the universal hardness of the transparent polypyropylene-based resin layer was fixed to 40 N / mm 2 and the thickness was distributed.

  The scratch resistance (pencil hardness) of the produced floor decorative material was evaluated. The evaluation results are shown in Table 2 below.

Experimental example 3
(Preparation of decorative sheet for flooring)
A 0.06 mm thick colored polypropylene film (base material sheet) was printed to form a pattern layer.

Next, a film (two-layer structure: layer thickness 0.3 mm) obtained by co-extrusion of the upper polypropylene layer having a universal hardness of 40 N / mm 2 and the lower polypropylene layer having a thickness of 0.15 mm distributed with a urethane-based dry laminate adhesive is used. Glued.

Next, an electron beam curable transparent surface protective layer (15 μm) having a universal hardness of 170 N / mm 2 was formed on the upper polypropylene layer.

Subsequently, embossing was given from the transparent surface protective layer side, and the decorative sheet for flooring was produced. (Preparation of decorative materials for floors)
A 12 mm lauan plywood was attached to the base sheet side of the decorative sheet for flooring to produce a decorative material for flooring. For the sticking, urethane-modified ethylene / vinyl acetate emulsion adhesive (100 g / m 2 wet) was used.
(Scratch resistance of flooring cosmetics)
The floor decorative material thus produced was evaluated for scratch resistance (pencil hardness, Hoffman scratch, Clemens scratch). The evaluation results are shown in Table 3 below.

Experimental Example 4
Experimental example except that the upper polypropylene layer HU was fixed at 40 N / mm 2 and the lower polypropylene layer HU was fixed at 15 N / mm 2 and co-extruded and the upper and lower layers were combined to 0.3 mm. In the same manner as in No. 3, a floor decorative material was produced.
(Scratch resistance of flooring cosmetics)
The floor decorative material thus produced was evaluated for scratch resistance (pencil hardness, Hoffman scratch, Clemens scratch). The evaluation results are shown in Table 4 below.

  The evaluation results when the thickness of the upper PP layer is 100 μm and the thickness of the lower PP layer is 50 μm are also shown at the end of Table 4. The evaluation results show that even when the upper PP layer is 100 μm and the lower PP layer is 50 μm, it is highly useful as a decorative sheet for flooring.

Experimental Example 5
Except for fixing the lower polypropylene layer to HU: 15 N / mm 2 and a thickness of 50 μm, distributing the thickness of the upper polypropylene layer (HU: 40 N / mm 2 ), co-extruding both layers, and sheeting, similar to Experimental Example 3 Thus, a flooring decorative material was produced.
(Scratch resistance of flooring cosmetics)
The floor decorative material thus produced was evaluated for scratch resistance (pencil hardness, Hoffman scratch, Clemens scratch). The evaluation results are shown in Table 5 below.

(Shock resistance of floor cosmetics)
The impact resistance of the decorative materials (3 types) shown in Table 5 was evaluated using a DuPont impact tester (based on JIS K 5600-5-3). Specifically, evaluation was performed by dropping a weight having a specified weight from a height of 30 cm onto the surface of the decorative material and measuring the amount of dents. The evaluation results are shown in Table 6 below.

  The floor material having the conventional backer has a dent amount of about 250 μm by the same impact test, and it can be seen that the floor decorative material of the present invention has substantially the same impact resistance. In the case of the conventional veneer flooring, the surface is hard and it is difficult to buffer the impact, so that the coating film is easily cracked and has a dent amount of about 400 μm.

Experimental Example 6
Experimental Examples 1 to 5 were performed by replacing the electron beam curable transparent surface protective layer with a transparent surface protective layer made of a two-component curable urethane resin.

  Each evaluation result was comparable to that shown in Tables 1-6. It has been found that the same effect can be obtained when the surface protective layer is formed from either an electron beam curable resin or a two-component curable urethane resin.

1. 1. Transparent surface protective layer Transparent polypropylene resin layer (upper polypropylene layer in Fig. 2)
3. 3. Pattern pattern layer and transparent adhesive layer 4. base material sheet 5. Adhesive layer Lauan plywood7. Lower polypropylene layer

Claims (4)

  1. On the base sheet made of polyolefin resin, there is a pattern layer, a transparent adhesive layer, a transparent polypropylene resin layer, and a transparent surface protective layer made of ionizing radiation curable resin or two-component curable urethane resin. It is a decorative sheet for flooring formed in order,
    (1) The thickness of the transparent polypropylene resin layer is 300 μm or more,
    (2) The universal hardness of the transparent polypropylene-based resin layer is 35 N / mm 2 or more, and (3) the universal hardness of the transparent surface protective layer is 100 N / mm 2 or more. .
  2.   The decorative sheet for flooring according to claim 1, wherein a colored concealing layer is further formed between the base sheet and the pattern layer.
  3.   The decorative sheet for flooring according to claim 1 or 2, wherein irregularities are formed on the front surface of the transparent surface protective layer.
  4.   The flooring decorative material formed by sticking the base material sheet side of the decorative sheet for flooring in any one of Claims 1-3 to a to-be-adhered material.
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JP6069868B2 (en) * 2011-03-31 2017-02-01 大日本印刷株式会社 Floor decorative sheet and floor decorative material
JP6300427B2 (en) * 2011-03-31 2018-03-28 大日本印刷株式会社 Floor decorative material
JP5853816B2 (en) * 2011-03-31 2016-02-09 大日本印刷株式会社 Floor decorative sheet and floor decorative material
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US10202768B2 (en) * 2013-06-20 2019-02-12 Kronoplus Technical Ag Directly printed panel having a two-layer design
WO2015146217A1 (en) * 2014-03-26 2015-10-01 大日本印刷株式会社 Decorative sheet and decorative plate using same
JP2016199951A (en) * 2015-04-13 2016-12-01 株式会社アイエムアイ Rustic floor material and manufacturing method thereof
JP6102989B2 (en) * 2015-06-25 2017-03-29 大日本印刷株式会社 Floor decorative material
JP6056924B2 (en) * 2015-09-01 2017-01-11 大日本印刷株式会社 Decorative sheet and method for producing decorative plate
JP2016128645A (en) * 2016-02-16 2016-07-14 大日本印刷株式会社 Decorative material for floor

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