JP2016211367A - Decorative sheet and decorative material for floor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet and a decorative material for a floor that offer high scratch resistance without impairing impact resistance and pollution resistance, especially under a high loading condition, at the same time suppressing remaining of a solvent in a surface protection layer.SOLUTION: A decorative sheet for a floor has at least a transparent resin layer, a first surface protection layer, and a second surface protection layer laminated sequentially in that order on a base material sheet, and is characterized as follows: (1) the first surface protection layer has a layer thickness between 5 and 20 μm and a Martens hardness between 40 and 100 N/mm; (2) the second surface protection layer has a layer thickness between 5 and 20 μm and a Martens hardness between 110 and 160 N/mm; and (3) a total of the layer thickness of the first surface protection layer and the thickness of the second surface protection layer is between 20 and 40 μm.SELECTED DRAWING: None

Description

  The present invention relates to a floor decorative sheet and a floor decorative material.

  Conventionally, in order to improve the scratch resistance of a decorative sheet for flooring, a method of applying an ionizing radiation curable resin to a surface protective layer and curing it is known. However, even such a decorative sheet for floors does not scratch the surface protective layer at all, and there is a problem that the scratch is caused when the scratch test is performed under a high load condition.

  Moreover, in order to further improve the scratch resistance of the floor decorative sheet under high load conditions, a method of increasing the hardness by increasing the surface protective layer thickness is known. However, if the surface protective layer is too thick and too hard, the impact resistance against falling objects and the like deteriorates, and there is a problem that the coating film breaks.

  On the other hand, if a soft resin is used for the surface protective layer in order to improve the impact resistance, the scratch resistance and the stain resistance are lowered.

  Further, when the thickness of the surface protective layer is increased, the solvent contained in the resin composition for forming the surface protective layer becomes difficult to dry, and as a result, there is a problem that the solvent remains in the surface protective layer. .

  As a decorative sheet with improved impact resistance and scratch resistance, two or more resin layers are laminated on the base sheet, and the glass transition point of the resin that forms the lower layer is higher than the glass transition point of the resin that forms the upper layer. Low decorative sheets have been proposed (see, for example, Patent Documents 1 to 3).

  However, in these decorative sheets, the layer structure of the surface protective layer has not been sufficiently studied, and the hardness and thickness of the layer used as the surface protective layer have not been studied. Even when these decorative sheets are used as a flooring, there is a problem in that they cannot exhibit properties excellent in stain resistance and scratch resistance without deteriorating impact resistance.

JP 2001-287314 A Japanese Patent Application Laid-Open No. 2004-31496 JP 2005-1119020 A

  The present invention is a floor in which contamination resistance and scratch resistance, in particular scratch resistance under high load conditions, are excellent, and solvent residue in the surface protective layer is suppressed without deteriorating impact resistance. It aims at providing the decorative sheet for floors, and the decorative material for floors.

  As a result of extensive research, the present inventors have a first surface protective layer and a second surface protective layer, and these show a specific layer thickness and Martens hardness, respectively. The inventors have found that the above object can be achieved by the sum of these layer thicknesses showing a specific value, and have completed the present invention.

That is, this invention relates to the following decorative sheets for floors.
1. A floor decorative sheet in which at least a transparent resin layer, a first surface protective layer, and a second surface protective layer are laminated in this order on a base sheet,
The first surface protective layer and the second surface protective layer contain an ionizing radiation curable resin,
(1) The first surface protective layer has a layer thickness of 5 to 20 μm and a Martens hardness of 40 to 100 N / mm ² .
(2) The second surface protective layer has a layer thickness of 5 to 20 μm and a Martens hardness of 110 to 160 N / mm ² .
(3) The floor decorative sheet, wherein the total thickness of the first surface protective layer and the layer thickness of the second surface protective layer is 20 to 40 μm.
2. Item 2. The floor decorative sheet according to Item 1, wherein the first surface protective layer contains a thermoplastic resin.
3. The floor decorative sheet according to Item 2, wherein the thermoplastic resin is at least one selected from an acrylic resin and a cellulose resin.
4). Item 4. The floor decorative sheet according to Item 2 or 3, wherein the thermoplastic resin has a weight average molecular weight of 4000 to 16000.
5. The said decorative sheet for floors in any one of said claim | item 2-4 whose glass transition temperature is 10-120 degreeC.
6). The floor decorative sheet according to any one of Items 1 to 5, further comprising a primer layer between the first surface protective layer and the second surface protective layer.
7). The floor decorative material formed by bonding the base sheet side of the decorative sheet for floor according to any one of Items 1 to 6 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 of the present invention is a decorative sheet for flooring in which at least a transparent resin layer, a first surface protective layer, and a second surface protective layer are laminated in this order on a base material sheet,
The first surface protective layer and the second surface protective layer contain an ionizing radiation curable resin,
(1) The first surface protective layer has a layer thickness of 5 to 20 μm and a Martens hardness of 40 to 100 N / mm ² .
(2) The second surface protective layer has a layer thickness of 5 to 20 μm and a Martens hardness of 110 to 160 N / mm ² .
(3) The total thickness of the first surface protective layer and the layer thickness of the second surface protective layer is 20 to 40 μm.

The decorative sheet for floors of the present invention having the above characteristics is hard because the Martens hardness of the second surface protective layer laminated as the upper layer of the first surface protective layer is 110 to 160 N / mm ² , particularly scratch resistance, Excellent scratch resistance under high load conditions and excellent contamination resistance. Moreover, since the layer thickness of the 2nd surface protective layer is limited to 5-20 micrometers, the crack by the fall of impact resistance resulting from layer thickness being too thick is suppressed. Moreover, since the Martens hardness of the 1st surface protective layer laminated | stacked as a lower layer of a 2nd surface protective layer is 40-100 N / mm < ² >, it is soft and is excellent in impact resistance. Moreover, since the layer thickness of the first surface protective layer is limited to 5 to 20 μm, it is not too soft, large dents due to impact from the surface are suppressed, and scratch resistance is excellent. Furthermore, since the total thickness of the first surface protective layer and the second surface protective layer is 20 to 40 μm, scratch resistance and contamination resistance under high load conditions required for a decorative sheet for flooring And impact resistance can all be satisfied. Since the first surface protective layer and the second surface protective layer contain an ionizing radiation curable resin, it is possible to easily obtain a decorative sheet for floors excellent in impact resistance, stain resistance, and scratch resistance. it can. Furthermore, since the layer thicknesses of the first surface protective layer and the second surface protective layer are as described above, it is possible to suppress the remaining of the solvent in the first surface protective layer and the second surface protective layer. .

  In addition, the Martens hardness in this specification is a value measured using a surface film physical property tester (PICODETOR HM-500, manufactured by Fisher Instruments Co., Ltd.), and a specific measuring method is as follows. It is.

That is, in the measurement method described above, the diamond indenter (Vickers indenter) shown in FIG. 1A is used to push the diamond indenter into the measurement sample as shown in FIG. The surface area A (mm ² ) is calculated from the length of the diagonal line, and the hardness is obtained by dividing the test load F (N). As shown in FIG. 1 (c), the indentation condition was that a load of 0 to 5 mN was first applied for 10 seconds, then held at a load of 5 mN for 5 seconds, and finally 5 Unloading to ~ 0mN is performed in 10 seconds. And the hardness calculated | required by F / A based on the surface area A and the test load F is the said Martens hardness (N / mm < ² >).

  Moreover, in this specification, in order to avoid the influence of the hardness of layers other than the said layer, the Martens hardness of the cross section of a surface protective layer and a transparent resin layer was measured. In this case, the floor decorative sheet is embedded with a resin (cold-curing type epoxy two-component curable resin), allowed to stand at room temperature for 24 hours or more and then cured, and then the cured embedded sample is mechanically polished to surface. By exposing the cross section of the protective layer and the transparent resin layer, and pressing the diamond indenter into the cross section of each layer (when fine particles such as inorganic fillers are included in the surface protective layer, each layer is pressed) The Martens hardness of the cross section was measured.

Surface Protective Layer In the floor decorative sheet of the present invention, at least a transparent resin layer, a first surface protective layer, and a second surface protective layer are laminated in this order on a base sheet.
(First surface protective layer)
The first surface protective layer has a layer thickness of 5 to 20 μm because it imparts impact resistance to the surface of the decorative sheet for flooring and suppresses the residual solvent in the first surface protective layer. It is preferable that it is 10-20 micrometers, and it is more preferable that it is 10-15 micrometers.

The first surface protective layer has a Martens hardness of 40 to 100 N / mm ² because it imparts impact resistance to the floor decorative sheet surface. It is preferably 40~70N / mm ^2, more preferably 40~50N / mm ^2.

  The Martens hardness can be appropriately set by 1) mixing two or more kinds of resins having different hardnesses, 2) mixing an elastomer with the resin, and the like. In addition, since the first surface protective layer uses an ionizing radiation curable resin, the number of polymerizable functional groups in one molecule is changed, or a resin having a different number of functional groups is used. It is also possible to adjust the Martens hardness to a desired value by, for example.

  The first surface protective layer contains an ionizing radiation curable resin. Substantially, those formed from ionizing radiation curable resins are preferred. When the first surface protective layer is formed of a resin containing an ionizing radiation curable resin, it is easy to improve the impact resistance and scratch resistance of the decorative sheet.

  The ionizing radiation curable resin is not particularly limited, and a prepolymer (including an oligomer) and / or a monomer containing a functional group capable of undergoing a polymerization and crosslinking reaction by irradiation with ionizing radiation such as ultraviolet rays and electron beams as a main component. A transparent resin 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 first surface protective layer 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 first surface protective layer can contain a thermoplastic resin. By containing a thermoplastic resin, it becomes possible to improve adhesiveness with a 2nd surface protective layer.

The thermoplastic resin is preferably at least one selected from acrylic resins and cellulose resins. By using at least one selected from an acrylic resin and a cellulose resin as the thermoplastic resin, the adhesion between the first surface protective layer and the second surface protective layer can be further improved.

  That is, by using at least one selected from an acrylic resin and a cellulose resin as the thermoplastic resin, the first surface protective layer is inhibited from crosslinking, and the crosslinking with the second surface protective layer is promoted. Can do.

  In addition, the solvent resistance of the first surface protective layer can be reduced, and the surface of the first surface protective layer becomes rough due to the solvent used in the second surface protective layer, and the surface of the rough first surface protective layer becomes The anchor effect by what is called a solvent attack which adhesiveness improves by laminating | stacking 2 surface protective layers can be promoted.

  Examples of the acrylic resin include polyurethane-polyacrylic resin, polyacrylamide resin, poly (meth) acrylic resin, (meth) acrylic resin, polyurethane-polyacrylic resin modified or mixed resin, polyester-acrylate resin. Examples thereof include resins.

  Specific examples of the acrylic resin include N-acryloyloxyethyl hexahydroimide, 2-hydroxy-3-phenoxypropyl acrylate, and isobornyl acrylate.

  Examples of the cellulose-based resin include cellulose ester, cellulose acetate, cellulose nitrate, cellulose acetate butyrate, and cellulose ether. Among them, the adhesion between the first surface protective layer and the second surface protective layer is further improved. It is more preferable to use cellulose acetate butyrate because it can be used.

  The content of the thermoplastic resin is preferably 0.5 to 5.0 parts by weight with respect to 100 parts by weight of the resin composition forming the first surface protective layer, and 1.0 to 2.0 parts by weight. More preferably, it is a part. When there is too much content of the said thermoplastic resin, even if it irradiates an electron irradiation line, there exists a possibility that a 1st surface protective layer may not fully harden | cure. When there is too little content of the said thermoplastic resin, there exists a possibility that the effect by adding the thermoplastic resin of improving the adhesiveness of a 1st surface protective layer and a 2nd surface protective layer cannot fully be exhibited.

  The thermoplastic resin preferably has a glass transition temperature (hereinafter referred to as Tg) of 10 to 120 ° C, and more preferably 50 to 120 ° C. If the Tg is too high, the solvent resistance is increased, and there is a possibility that the effect of improving the adhesion between the first surface protective layer and the second surface protective layer cannot be sufficiently exhibited. The compatibility with the ionizing radiation curable resin contained in the layer is poor, and the first surface protective layer may become cloudy.

  Moreover, it is preferable that the weight average molecular weights of the said thermoplastic resin are 4000-16000, and it is more preferable that it is 10000-16000. If the weight average molecular weight is too large, the solvent contained in the ionizing radiation curable resin contained in the first surface protective layer becomes difficult to dry and the residual solvent amount increases, The surface protective layer may not be cured sufficiently. If the weight average molecular weight is too small, the compatibility with the ionizing radiation curable resin contained in the first surface protective layer is poor, and the first surface protective layer may become cloudy.

The first surface protective layer is, for example, a known coating method such as gravure coating or roll coating with a two-component curable urethane resin containing an ionizing radiation curable resin or an ionizing radiation curable resin on a transparent polypropylene resin layer. After coating, it can be formed by curing the resin. In the case of an ionizing radiation curable resin, the resin is cured by electron beam irradiation.
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.

(Second surface protective layer)
The second surface protective layer exhibits scratch resistance under a relatively high load, the surface protective layer is not fragile, has excellent impact resistance, and has excellent contamination resistance. Also, the second surface protective layer The layer thickness is 5 to 20 μm for the purpose of suppressing the remaining of the solvent. It is preferable that it is 10-20 micrometers, and it is more preferable that it is 10-15 micrometers.

The second surface protective layer exhibits mar resistance under relatively high loads, while the surface protective layer is not fragile, has excellent impact resistance, and further has excellent contamination resistance. 110 to 160 N / mm ² . Among these ranges, 110 to 130 N / mm ² is preferable.

  Other configurations of the second surface protective layer are the same as those of the first surface protective layer described above.

  The total thickness of the first surface protective layer and the layer thickness of the second surface protective layer is 20 to 40 μm. By making the total layer thickness within the above range, the surface protective layer can satisfy all of scratch resistance, stain resistance and impact resistance under the high load conditions required for a decorative sheet for floors. Furthermore, it becomes possible to suppress the residual solvent in the first surface protective layer and the second surface protective layer.

  The total thickness of the first surface protective layer and the second surface protective layer is preferably 25 to 35 μm.

Base sheet The floor decorative sheet of the present invention includes a base sheet, and a transparent resin layer, the first surface protective layer, and the second surface protective layer are laminated on the surface (front surface). The

  As a base material sheet, what was formed, for example with the thermoplastic resin is suitable. Specifically, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer Examples thereof include polymers, ionomers, polyacrylic acid esters, and polymethacrylic acid esters. Among these, polyolefins such as polypropylene are preferable.

  The base material sheet may be colored. In this case, a coloring material (pigment or dye) can be added to the above thermoplastic resin for coloring. As the colorant, for example, inorganic pigments such as titanium dioxide, carbon black and iron oxide, organic pigments such as phthalocyanine blue, and various dyes can be used. These can be selected from one or more known or commercially available ones. Further, the addition amount of the colorant may be appropriately set according to the desired color tone.

  The base sheet contains various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, UV absorbers, and light stabilizers as necessary. It may be.

Examples of the filler include silica, clay, calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. By including a filler, an effect of suppressing see-through, an effect of improving surface characteristics, and the like are obtained. About 0-100 weight part is preferable with respect to 100 weight part of resin components, and, as for content of a filler, about 10-50 weight part is more preferable.

  Although the thickness of a base material sheet can be suitably set with the use of a final product, a usage method, etc., generally 50-250 micrometers is preferable.

  If necessary, the base sheet may be subjected to corona discharge treatment on the surface (front surface) in order to enhance the adhesion of the ink for forming the pattern layer. What is necessary is just to implement the method and conditions of a corona discharge process according to a well-known method. Moreover, you may give a corona discharge process to the back surface of a base material sheet as needed.

Back surface primer layer A back surface primer layer may be provided on the back surface of the above-described base material sheet, if necessary. For example, it is advantageous when a decorative material for floors is produced by bonding a base sheet and an adherend.

  A back surface primer layer can be formed by apply | coating a well-known primer agent to the back surface of a base material sheet. Examples of the primer agent include a urethane resin-based primer agent made of an acrylic-modified urethane resin (acrylic urethane-based resin), a urethane-cellulose resin (for example, a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton) ), A resinous primer agent made of a block copolymer of acrylic and urethane, and the like. You may mix | blend an additive with a primer as needed. Examples of the additive include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The blending amount of the additive can be appropriately set according to the product characteristics.

  Although the thickness of a back surface primer layer is not specifically limited, Usually, 0.1-10 micrometers, Preferably it is about 1-5 micrometers.

A primer layer for forming a pattern / pattern layer Further, a primer layer for forming a pattern / pattern layer may be provided on the surface (front surface) of the above-described base material sheet, if necessary. For example, it is advantageous when a decorative material for floors is produced by bonding a base sheet and a pattern layer.

  The primer layer for forming the pattern / pattern layer can be formed by applying a known primer agent to the surface (front surface) of the base sheet. As a primer agent, the same thing as what is used for the above-mentioned back surface primer layer can be used.

  The thickness of the primer layer for forming the pattern / pattern layer is not particularly limited, but is usually 0.1 to 10 μm, preferably about 1 to 5 μm.

Pattern Pattern Layer The decorative sheet for floors of the present invention may be provided with a pattern pattern layer on the surface (front surface) of the base sheet, if desired.

  The design pattern layer imparts a desired design (design) to the floor decorative sheet, and the type of design 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.

  The method for forming the pattern layer is not particularly limited. For example, printing using ink 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 in the base-material sheet | seat surface by a method.

  Examples of the colorant include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, and 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.

  As binder resin, polyester urethane resin, polyester urethane resin with hydrophilic treatment, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate A polymer, a rosin derivative, an alcohol adduct of a styrene-maleic anhydride copolymer, a cellulose resin, or the like can be used in combination.

  More specifically, for example, polyurethane-polyacrylic resin, polyacrylamide resin, poly (meth) acrylic acid resin, polyethylene oxide resin, poly N-vinylpyrrolidone resin, water-soluble polyester resin, water-soluble Polyamide resins, water-soluble amino resins, water-soluble phenol resins, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, polysaccharides, etc. can be used. Further, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin modified or mixed resin, and other resins can also be used. The binder resin can be used alone or in combination 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 (also referred to as a colored concealment layer), for example, a gravure coating method, a gravure reverse coating method, a roll coating method, a knife coating method, an air knife coating method, a die coating Various coating methods such as a method, a lip coat method, a comma coat method, a kiss coat method, a flow coat method, and a dip coat method are also included.

  In addition to the above, for example, 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. are used or combined with other forming methods. It may be used.

  The thickness of the pattern layer is not particularly limited and can be appropriately set 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.

Adhesive layer The floor decorative sheet of the present invention may be provided with an adhesive layer between the pattern layer and the transparent resin layer, if desired.

The adhesive layer may be transparent or translucent as long as the pattern layer can be recognized. Moreover, the adhesive agent used by an adhesive bond layer is not specifically limited, According to the component etc. which comprise a pattern layer or a transparent resin layer, it can select suitably. Examples of the adhesive known in the field of floor decorative sheets include thermoplastic resins such as polyamide resins, acrylic resins and vinyl acetate resins, and thermosetting resins such as urethane resins. These adhesives are used individually by 1 type or in combination of 2 or more types. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied.

  Moreover, well-known easy adhesion processes, such as a corona discharge process, a plasma process, a degreasing process, and a surface roughening process, can also be given to an adhesion surface as needed.

  The adhesive layer can be formed, for example, by applying the adhesive on the pattern layer, drying it once, and then laminating a transparent resin. The method for applying the adhesive is not particularly limited. For example, roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, comma coating, etc. The method can be adopted.

  The thickness of the adhesive layer varies depending on the transparent protective layer, the type of adhesive used, and the like, but generally may be about 0.1 to 30 μm.

Transparent resin layer In the decorative sheet for floor of the present invention, a transparent resin layer is laminated between the surface (front surface) of the base sheet and the first surface protective layer.

  The resin constituting the transparent resin layer is not limited as long as it is transparent when the lower pattern pattern layer is present, or is translucent within a range where the lower pattern pattern layer can be visually recognized. Examples of such resins include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-acrylic acid ester copolymer. , Ionomer, polymethylpentene, polyacrylate, polymethacrylate, polycarbonate, cellulose triacetate and the like. The said resin can be used individually or in combination of 2 or more types. Moreover, the copolymer which has these resins as a main component can also be used.

  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.

  As the polyolefin resin, either a homopolymer or a copolymer can be used. For example, in the case of a polypropylene resin, homopolypropylene resin, random polypropylene resin, block polypropylene resin and the like can be mentioned. As the polyolefin resin, a commercially available product (for example, Prime Polymer Co., Ltd. (Prime TPO “J-5900”, Prime Polypro “F219DA”), etc.) can be used.

  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.

  The thickness of the transparent resin layer is not particularly limited, but if the thickness of the transparent resin layer is too thin, the wear resistance is lowered. On the other hand, if it is too thick, problems such as fluffing at the time of cutting occur, preferably less than 150 μm, more preferably 40-100 μm, and even more preferably 60-80 μm.

  If necessary, the transparent resin layer may be subjected to corona discharge treatment on the surface (front surface) in order to enhance the adhesion with the upper primer layer.

Primer layer In the floor decorative sheet of the present invention, a primer layer may be provided between the transparent resin layer and the first surface protective layer, if desired. The primer layer has a function of improving the adhesion (adhesion) between the transparent resin layer and the surface protective layer. Moreover, it has the effect of making it hard to produce a fine crack and whitening in the extending | stretching part of a surface protective layer. Further, the provision of the primer layer facilitates the formation of the surface protective layer. The primer layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and translucent.

  The primer layer can be formed by applying a known or commercially available primer on the transparent resin layer. In particular, the primer layer is preferably a layer formed by crosslinking a resin. Examples of the primer agent for forming such a layer include a urethane resin primer agent made of an acrylic-modified urethane resin and the like, a resin primer agent made of a block copolymer of acrylic and urethane, and the like. These primer agents are used alone or in combination of two or more.

The primer layer may contain silica as a matting agent. The content of silica in the primer agent is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the resin component,
10-40 weight part is more preferable. Furthermore, you may make a primer agent contain a well-known additive as needed. For example, the adhesiveness of the said transparent resin layer and the said surface protective layer can be improved more by making a primer agent contain a hexamethylene diisocyanate type hardening | curing agent. Various kinds of weathering agents such as ultraviolet absorbers and light stabilizers may be added to the primer layer.

  The primer layer can be formed by a direct coating method, for example, gravure coating, gravure reverse coating, gravure offset coating, spin coating, roll coating, reverse roll coating, kiss coating, wheeler coating, dip coating, solid coating by silk screen, wire A bar coat, a flow coat, a comma coat, a pouring coat, a brush coat, a spray coat, etc. can be used.

  The thickness of the primer layer is preferably about 0.1 to 10 μm. When it is 0.1 μm or more, the effect of preventing the surface protective layer from cracking, breaking, whitening, etc. can be sufficiently exerted. On the other hand, if the thickness of the primer layer is 10 μm or less, when the primer layer is applied, the coating film is stable in drying and curing, so that the moldability does not fluctuate. From the above points, the thickness of the primer layer is more preferably 0.1 to 10 μm.

Manufacturing method of decorative sheet for floor The lamination of each layer constituting the decorative sheet for floor of the present invention includes, for example, (a) a back primer layer provided on the back surface of the base sheet, and (a) the front surface of the base sheet (C) an adhesive layer is formed on the pattern printed pattern layer, (d) a transparent resin layer is extruded and laminated on the adhesive layer by the laminating method, E) After applying a corona discharge treatment to the surface of the transparent resin layer, a primer layer is formed, and (f) the first surface of the present invention having a specific layer thickness and Martens hardness by gravure coating on the surface. The second surface protection of the present invention having a specific layer thickness and Martens hardness on the surface by applying an ionizing radiation curable resin for forming a protective layer and irradiating with an electron beam. Ionizing radiation curable resin to form a layer And Engineering, by irradiating an electron beam, can be performed.

The embossed floor decorative sheet may be embossed from the transparent resin layer side, the first surface protective layer side, or the second surface protective layer side.

  Embossing is performed to give a desired texture such as a wood grain pattern to the decorative sheet for flooring. For example, after the surface protective layer is heated and softened, it is pressed and shaped with an embossed plate having a concavo-convex pattern of a desired shape, and then textured by cooling and fixing. Embossing can be performed with a known single wafer or rotary embossing machine. Examples of the embossed concavo-convex pattern include a wood grain conduit groove, a float pattern (a concavo-convex pattern of a raised annual ring), a hairline, a grain, and a satin texture.

  When embossing is performed, the embossed recess may be filled with ink by wiping as necessary. For example, the embossed recess is filled with ink while scratching the surface with a doctor blade. As the ink to be filled (wiping ink), usually, an ink having a two-component curable urethane resin as a binder can be used. In particular, by performing a wiping process on the grain conduit groove irregularities, the product value can be increased by expressing a design closer to the actual grain.

You may provide a backer layer in the back surface of a base material sheet in the decorative sheet for backer layer floors.

  The resin constituting the backer layer is not limited, but is preferably a thermoplastic resin, for example, polyethylene, polypropylene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, amorphous polyethylene terephthalate. (A-PET), highly heat-resistant polyalkylene terephthalate [for example, polyethylene terephthalate in which a part of ethylene glycol is substituted with 1,4-cyclohexanedimethanol, diethylene glycol or the like, so-called trade name PET-G (Eastman Chemical) Company)), polybutylene terephthalate, polycarbonate, polyarylate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer Polyimide, polystyrene, polyamide, ABS (acrylonitrile - butadiene - styrene copolymer) and the like. These resins can be used alone or in combination of two or more.

  The thickness of the backer layer can be appropriately set depending on the use of the final product, the method of use, etc., but generally it is preferably 50 to 800 μm.

  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.

  As a method for forming the backer layer, for example, it may be laminated on the transparent adhesive layer by a calendar method, an inflation method, a T-die extrusion method, or an existing film may be used.

  However, the floor decorative sheet of the present invention can ensure sufficient impact resistance without forming a backer layer.

Flooring decorative material The flooring decorative material of the present invention can be made into a flooring decorative material by bonding and adhering the adherend to the base sheet side of the flooring decorative sheet of the present invention.

The material of various adherends is not particularly limited, and examples thereof include inorganic non-metallic materials, metallic materials, woody 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.

  In order to bond the adherend and the decorative sheet, for example, an adhesive can be used. 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 joining the adherend and the decorative sheet, for example, according to the characteristics of the final product, cutting, use of a tenoner, sane processing, provision of V-shaped grooves, chamfering on four sides, and the like may be performed.

  The decorative sheet for floor according to the present invention includes a first surface protective layer and a second surface protective layer, which contain an ionizing radiation curable resin and have a layer thickness and a Martens hardness within a specific range, and are provided with a first surface protective layer. Since the total thickness of the layer and the second surface protective layer is within a specific range, the contamination resistance and the scratch resistance, particularly the scratch resistance under high load conditions, without deteriorating the impact resistance. In addition, the residual of the solvent in the surface protective layer is suppressed.

It is a figure which shows the diamond indenter (a) used for the measurement of the Martens hardness in this specification, the schematic diagram (b) of pushing operation, and an example (c) of pushing load and displacement. It is a figure which shows an example (layer structure conceptual diagram) of embodiment of the decorative sheet for floors of this invention, and the decorative material for floors.

  Next, the present invention will be specifically described with reference to experimental examples. However, the present invention is not limited to the examples.

Examples and Comparative Examples (Example 1)
Corona discharge treatment was applied to both surfaces of a base sheet made of a colored polypropylene film having a thickness of 60 μm, and a back primer layer having a thickness of 2 μm was formed on the back surface. Next, a pattern pattern layer having a thickness of 2 μm was formed on the front surface of the base sheet by printing, and a transparent adhesive layer was further formed on the pattern print pattern layer. On the transparent adhesive layer, transparent thermoplastic polyolefin was heated and melt extruded by a T-die extruder to form a transparent resin layer having a thickness of 80 μm. After the surface of this transparent resin layer was subjected to corona discharge treatment, a primer layer was formed by applying a two-component curable urethane resin (urethane / acrylic copolymer).

On the surface, an ionizing radiation curable resin having the following composition as a main component was applied by a gravure coating method to a thickness of 5 μm and dried to form an uncured ionizing radiation curable resin layer. Next, in an atmosphere with an oxygen concentration of 100 ppm or less, the uncured ionizing radiation curable resin layer is cured by irradiating with an electron beam under the conditions of an acceleration voltage of 175 keV and 2 Mrad (20 kGy) using an electron beam irradiation apparatus. By doing so, a first surface protective layer was formed.

  Further, an ionizing radiation curable resin having the following composition as a main component is applied to the surface of the first surface protective layer with a thickness of 15 μm by a gravure coating method, dried, and uncured ionizing radiation curable resin. A layer was formed. Next, in an atmosphere having an oxygen concentration of 100 ppm or less, the uncured ionizing radiation curable resin layer is cured by irradiating an electron beam under the conditions of an acceleration voltage of 175 keV and 5 Mrad (50 kGy) using an electron beam irradiation apparatus. By doing so, a second surface protective layer was formed.

  The composition of the main component of the ionizing radiation curable resin is as follows.

First surface protective layer , bifunctional urethane acrylate oligomer A (weight average molecular weight 1500) 100 parts by weight, matting agent (average particle size 11 μm silica) 8 parts by weight, solvent (ethyl acetate) 100 parts by weight
Second surface protective layer , bifunctional urethane acrylate oligomer A (weight average molecular weight 1500) 80.0 parts by weight, hexafunctional urethane acrylate oligomer (weight average molecular weight 1500) 20.0 parts by weight, matting agent (average particle diameter 11 μm silica) 8 parts by weight / solvent (ethyl acetate) 100 parts by weight The floor decorative sheet of Example 1 was produced as described above. The Martens hardness in the cross-sectional direction of the first surface protective layer is 40 N / mm ² (average value of 10 measured values), and the Martens hardness in the cross-sectional direction of the second transparent resin layer is 110 N / mm ² (10 The average value of the measured points).

(Examples 2-13, Comparative Examples 1-13)
For floors of Examples 2 to 13 and Comparative Examples 1 to 13, except that the thicknesses of the first surface protective layer and the second surface protective layer were changed as shown in Tables 2 and 3. A decorative sheet was prepared.

(Examples 14 to 28, Comparative Examples 14 to 33)
Examples 14 to 28 and comparison were made in the same manner as in Example 1 except that the layer thickness and Martens hardness of the first surface protective layer and the second surface protective layer were changed as shown in Tables 4 and 5. The floor decorative sheets of Examples 14 to 33 were prepared.

(Comparative Examples 34 to 51)
The decorative sheets for floors of Comparative Examples 34 to 51 were prepared in the same manner as in Example 1 except that the surface protective layer was one layer and the layer thickness and Martens hardness of the surface protective layer were as shown in Table 6.

The following components were used as components constituting the ionizing radiation curable resin used in the above examples and comparative examples.
-Bifunctional urethane acrylate oligomer A (weight average molecular weight 1500) Tg = 25 ° C.
· Bifunctional urethane acrylate oligomer B (weight average molecular weight 5000) Tg = -55 ° C · 6 functional urethane acrylate oligomer (weight average molecular weight 1500) Tg = 200 ° C or higher However, bifunctional urethane acrylate oligomer is a radical in one molecule. It shall mean a urethane acrylate oligomer having two polymerizable acryloyl groups. The hexafunctional urethane acrylate oligomer means a urethane acrylate oligomer having six radical polymerizable acryloyl groups in one molecule.

(Evaluation method)
About the test of following (1)-(4), the produced floor decorative sheet was bonded together on the medium density wood fiber board (MDF) of thickness 2.7mm. Moreover, about the test of following (5), the produced floor decorative sheet was used without bonding to MDF.

(1) Light load scratch resistance test (Hoffman scratch test)
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 surface of the floor decorative sheet 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 sheet for flooring.

The evaluation criteria are as follows.
○: Scratches are not seen at 1500 g load or more. Δ: Scratches are not seen at 1000 g load or more. ×: Scratches are generated at less than 1000 g load.
(2) High load scratch resistance test (coin scratch test)
Two coins (10-yen coins) were set so as to contact at an angle of 45 ° (two-point support), and the tester was moved on the decorative material. The load (weight) was gradually increased, and the test was conducted until the surface of the decorative sheet was scratched or indented.

The evaluation criteria are as follows.
◎: No scratches observed at 7 kg load ○: No scratches observed at 5 kg load Δ: No scratches observed at 4 kg load ×: Scratches occurred below 4 kg load
(3) Impact resistance test (DuPont impact test)
According to the DuPont impact test of JISK5600, a shooting die having a hemispherical tip with a radius of 6.3 mm was allowed to stand on the surface of the decorative sheet for floors obtained in Examples and Comparative Examples, and a load of 500 g was applied on the shooting die. The weight was evaluated by dropping from a height of 300 mm.

The evaluation criteria are as follows.
○: Dropped from a height of 300 mm, and the cracks in the decorative sheet for flooring could not be observed by visual observation Δ: Dropped from a height of 300 mm, and the cracks in the decorative sheet for flooring were slightly observed by visual inspection Tuna x: Dropped from a height of 300 mm and visually observed cracks in the decorative sheet for flooring
(4) Stain resistance test The stain resistance of the floor decorative sheets produced in the examples and comparative examples was evaluated by the following test. That is, a pilot company red ink was applied directly on a decorative sheet for flooring, and a watch glass was put on. After leaving it for 6 hours, it was wiped with a cloth impregnated with ethanol and observed.

The evaluation criteria are as follows.
○: No contamination remaining
Δ: Contamination residue was slight
×: There was a clear contamination residue
(5) Residual solvent amount Within 1 hour from the preparation of the test floor decorative sheet, the floor decorative sheet was cut into a rectangular shape having a width of 5 cm and a length of 10 cm to prepare a test piece. The test piece is sealed in a glass container and 120 ° C.
The solvent was diffused in the glass container by heating for 7 minutes at a temperature of 5 to evaporate the solvent remaining on the test piece. The amount of the solvent present in a vaporized state in the glass container was measured by gas chromatography, and the amount of the residual solvent was measured by converting it to the amount of solvent per 1 m ^{2 of the} decorative sheet for floor.

  In addition, the measurement conditions of gas chromatography are as follows.

Measuring instrument device: Headspace gas chromatograph (manufactured by Shimadzu Corporation HSS-4A GC-17A)
Column: DB-624 (30 m × 0.53 mm ID 3 μm)
Sample size: 5cm x 10cm 1 vial size: 27ml
Analytical heating condition : 120 ° C-7min
Oven: 35 ° C-8min hold-9 ° C / min-135 ° C-10min
The total amount of all components (TVOC) detected up to 29 minutes at room temperature (unit: converted to mg / m ² ) was defined as the residual solvent amount.

  In addition, when an unknown component exists, it totaled in toluene conversion.

The evaluation criteria are as follows.
○: Residual solvent material of less than 500 mg / m ² ×: Residual solvent material of 500 mg / m ² or more Table 1 shows resin compositions and martens used in the first surface protective layer and the second surface protective layer. Indicates hardness. In Table 1, the bifunctional A, the bifunctional B, and the hexafunctional represent the bifunctional urethane acrylate oligomer A, the bifunctional urethane acrylate oligomer B, and the hexafunctional aliphatic urethane acrylate oligomer, respectively. Moreover, in Table 1, a numerical value represents a weight part.

  The evaluation results are shown in the following table.

Tables 2 and 3 show test examples when the Martens hardness of the first surface protective layer is 40 N / mm ² and the Martens hardness of the second surface protective layer is 110 N / mm ² . In Tables 2 and 3, the Martens hardness of the first surface protective layer and the second surface protective layer is fixed to the above value, and the thickness of each layer is changed, and the effect of the layer thickness on the performance of the decorative sheet for flooring. The test was conducted.

  As is clear from Tables 2 and 3, in Examples 1 to 13, the Martens hardness of each of the first surface protective layer and the second surface protective layer, the thickness of each layer, and the first surface protective layer and the second surface protective layer. Since the total thickness of the layers was an appropriate value, it was excellent in scratch resistance, impact resistance, and contamination resistance.

  On the other hand, from the results of Comparative Examples 2 and 3, when the thickness of the first surface protective layer is less than 5 μm, the impact absorbability is poor and the second surface protective layer is cracked, so that the impact resistance may be inferior. I understood. In Comparative Example 1, the thickness of the first surface protective layer is less than 5 μm, but the second surface layer is not too hard because the layer thickness is as thin as 15 μm, and cracking hardly occurs. It became.

  From the results of Comparative Examples 1, 4, and 6, it was found that the scratch resistance was poor when the total thickness of the first surface protective layer and the second surface protective layer was less than 20 μm.

  From the results of Comparative Examples 8, 10, and 12, it was found that the scratch resistance was poor when the thickness of the second surface protective layer was less than 5 μm.

  From the results of Comparative Examples 3, 5, 7, 9, 11, 12, and 13, when either one of the first surface protective layer and the second surface protective layer exceeds 20 μm, the first surface It was found that the amount of solvent contained in the protective layer and the second surface protective layer was increased, and the residual amount of solvent in the floor decorative sheet was increased.

  Table 4 shows test examples when the thickness of the first surface protective layer and the thickness of the second surface protective layer are 15 μm. In Table 4, the thickness of the first surface protective layer and the second surface protective layer is fixed to the above values, and the Martens hardness is changed to affect the effect of the Martens hardness on the performance of the decorative sheet for flooring. A test was conducted.

  As apparent from Table 4, in Examples 14 to 16, the Martens hardness of each of the first surface protective layer and the second surface protective layer, the thickness of each layer, and the first surface protective layer and the second surface protective layer. Since the total thickness of the layers was an appropriate value, it was excellent in scratch resistance, impact resistance, and contamination resistance.

On the other hand, from the results of Comparative Examples 14 to 17, if the Martens hardness of the first surface protective layer is less than 40 N / mm ² , the first surface protective layer as the lower layer is too soft and the dent is large, so that the scratch resistance It turned out to be inferior.

From the results of Comparative Examples 14, 18, 20, and 22, when the Martens hardness of the second surface protective layer is less than 110 N / mm ² , the surface of the decorative sheet for flooring is too soft and dirt easily adheres, and is resistant to contamination. It turned out to be inferior.

From the results of Comparative Examples 17, 19, 21, and 25, when the Martens hardness of the second surface protective layer exceeds 160 N / mm ² , the second surface protective layer is too hard and cracks are generated. It turned out to be inferior.

From the results of Comparative Examples 23 to 25, it is understood that when the Martens hardness of the first surface protective layer exceeds 100 N / mm ² , the first surface protective layer is too hard and has poor impact absorption and poor impact resistance. It was. In Comparative Example 22, although the Martens hardness of the first surface protective layer exceeds 100 N / mm ² , the Martens hardness of the second surface layer is as soft as 100 N / mm ^2, and thus the impact resistance evaluation result is Δ and became.

  In Table 5, the Martens hardness of the 1st surface protective layer and the 2nd surface protective layer is made into the value shown in Table 5, and the layer thickness of the 1st surface protective layer and the layer thickness of the 2nd surface protective layer are 5- A test example was shown in the case of changing in the range of 20 μm. In Table 5, with respect to the first surface protective layer and the second surface protective layer, the Martens hardness and the layer thickness were changed, and the effects of these physical properties on the performance of the floor decorative sheet were tested.

  As apparent from Table 5, in Examples 17 to 28, the Martens hardness of the first surface protective layer and the second surface protective layer, the thickness of each layer, and the first surface protective layer and the second surface protective layer. Since the total thickness of the layers was an appropriate value, it was excellent in scratch resistance, impact resistance, and contamination resistance.

On the other hand, from the results of Comparative Examples 26, 28, 30, and 32, when the Martens hardness of the second surface protective layer exceeds 160 N / mm ² , the second surface protective layer is too hard and cracks occur. It was found to be inferior in impact.

From the results of Comparative Examples 27, 29, 31, and 33, the Martens hardness of the second surface protective layer exceeds 160 N / mm ² and the thickness of the second surface protective layer is as thin as about 5 to 10 μm. It was found that the scratch resistance was poor.

  Table 6 shows test examples when the surface protective layer is one layer.

  As is apparent from Table 6, in Comparative Examples 34 to 51, the surface protective layer is one layer, so that a floor decorative sheet satisfying all of scratch resistance, impact resistance, and stain resistance can be obtained. I found that there was no.

  In order to evaluate the adhesion between the first surface protective layer and the second surface protective layer of the floor decorative sheet of the present invention, floor decorative sheets of Examples 29 to 33 were prepared, and the following coating film adhesion test was performed. went.

(Examples 29 to 33)
Example 8 except that 1 part by weight of the acrylic resins A to D and the cellulose resin E in Table 7 was blended with respect to 100 parts by weight of the resin composition forming the first surface protective layer of Example 8. Similarly, floor decorative sheets of Examples 29 to 33 were produced.

  About these Examples 29-33, the following coating-film adhesiveness tests were done. Moreover, in Examples 29 to 33 used for the coating film adhesion test, the time (lead time) from the formation of the first surface protective layer to the formation of the second surface protective layer was set to the first time. Three types of decorative sheets for flooring were prepared immediately after the surface protective layer was formed, 24 hours later, and 72 hours later.

  Moreover, in the following coating-film adhesiveness test, it tested also about what produced the decorative sheet for floors of Example 8 similarly to Examples 29-33 for the comparison.

  In addition, among Examples 29 to 33, for the decorative sheet for floors on which the second surface protective layer was formed immediately after the formation of the first surface protective layer, the above (1) to (5) ) Was conducted.

(6) Double-sided tape was stuck on the entire back surface of the decorative sheet for coating film adhesion test floor, and it was pressure-bonded to a base (metal flat plate). Adhesive tape (Nichiban “Cello Tape (registered trademark)”, industrial width: 24 mm width) was attached to the front surface (surface protective layer) of the decorative sheet for flooring, and rubbed with a cotton cloth to ensure sufficient adhesion. Next, the attached adhesive tape was peeled off rapidly at a peeling angle of 45 °. After repeating the adhesion and peeling of the adhesive tape three times, the presence or absence of peeling of the surface protective layer was confirmed and evaluated by visual observation.

The evaluation criteria are as follows.
◯: not peeled off by Sero-UV (registered trademark) test after 200 hours of S-UV Δ: not peeled off by Cello-Tape (registered trademark) test in normal state ×: Cello-resistant tape (registered trademark) in normal state What caused peeling by test In addition, the said S-UV200-hour irradiation was performed on condition of the following. That is, the decorative sheet was tested according to JIS-B-7350 as an accelerated weather resistance test. Specifically, using a sunshine carbon arc lamp type weather resistance tester, the test was conducted for a total of 200 hours under the conditions of an illuminance of 60 mW / cm ² , a black panel temperature of 63 ° C., a tank humidity of 50% Rh, and a wet cycle of 20H / 4H. .

  The results are shown in Table 8.

  As is apparent from Table 8, the floor decorative sheets of Examples 29 to 33 were excellent in coating film adhesion because the first surface protective layer contained an acrylic resin or a cellulose resin. In particular, since the floor decorative sheets of Examples 32 and 33 use an acrylic resin or a cellulose resin having an appropriate weight average molecular weight, the lead time is immediately after the first surface protective layer is formed, after 24 hours, Excellent coating film adhesion was exhibited under all conditions after 72 hours.

  In addition, since the floor decorative sheets of Examples 29 to 31 have a lower weight average molecular weight of the acrylic resin than the floor decorative sheets of Examples 32 and 33, the ionizing radiation curable type contained in the first surface protective layer. The compatibility with the resin was slightly inferior, and the coating film adhesion after 72 hours was slightly inferior.

  On the other hand, since the decorative sheet for floors of Example 8 does not contain an acrylic resin and a cellulose resin in the first surface protective layer, the lead time is excellent in coating film adhesion under the conditions immediately after the formation of the first surface protective layer. However, under the conditions after 24 hours and after 72 hours, it was found that some peeling occurred in the cello-tape (registered trademark) test after irradiation with S-UV for 200 hours.

1. Floor decorative sheet2. 2. Back primer layer Base sheet 4. Pattern layer 5 5. Adhesive layer 6. Transparent resin layer Primer layer 8. First surface protective layer 9. Second surface protective layer

That is, this invention relates to the following decorative sheets for floors.
1. On the base sheet, a floor decorative sheet having at least a transparent resin layer, a first surface protective layer, and a second surface protective layer in this order,
The first surface protective layer and the second surface protective layer contain an ionizing radiation curable resin,
(1) The first surface protective layer has a layer thickness of 15 to 20 μm and a Martens hardness of 40 to 100 N / mm ² .
(2) the second surface protective layer has a thickness is 15 ～20Myuemu, and floor decorative sheet Martens hardness is characterized <br/> that Ru 110~160N / mm ² der.
2. Item 2. The floor decorative sheet according to Item 1, wherein the first surface protective layer contains a thermoplastic resin.
3. The floor decorative sheet according to Item 2, wherein the thermoplastic resin is at least one selected from an acrylic resin and a cellulose resin.
4). Item 4. The floor decorative sheet according to Item 2 or 3, wherein the thermoplastic resin has a weight average molecular weight of 4000 to 16000.
5. Item 4. The floor decorative sheet according to Item 2 or 3, wherein the thermoplastic resin has a weight average molecular weight of 10,000 to 16,000.
6 . Item 6. The floor decorative sheet according to any one of Items 2 to 5 , wherein the thermoplastic resin has a glass transition temperature of 10 to 120 ° C.
7 . Item 7. The floor decorative sheet according to any one of Items 1 to 6 , further comprising a primer layer between the first surface protective layer and the second surface protective layer.
8). Item 8. The floor decorative sheet according to any one of Items 1 to 7, further comprising a pattern layer between the base sheet and the transparent resin layer.
9 . Item 10. A floor decorative material having an adherend on the base sheet side of the floor decorative sheet according to any one of Items 1 to 8 .

Claims (7)

A floor decorative sheet in which at least a transparent resin layer, a first surface protective layer, and a second surface protective layer are laminated in this order on a base sheet,
The first surface protective layer and the second surface protective layer contain an ionizing radiation curable resin,
(1) The first surface protective layer has a layer thickness of 5 to 20 μm and a Martens hardness of 40 to 100 N / mm ² .
(2) The second surface protective layer has a layer thickness of 5 to 20 μm and a Martens hardness of 110 to 160 N / mm ² .
(3) The floor decorative sheet, wherein the total thickness of the first surface protective layer and the layer thickness of the second surface protective layer is 20 to 40 μm.   The said 1st surface protective layer is a decorative sheet for floors of Claim 1 containing a thermoplastic resin.   The floor decorative sheet according to claim 2, wherein the thermoplastic resin is at least one selected from an acrylic resin and a cellulose resin.   The decorative sheet for floor according to claim 2 or 3, wherein the thermoplastic resin has a weight average molecular weight of 4000 to 16000.   The flooring decorative sheet according to any one of claims 2 to 4, wherein the thermoplastic resin has a glass transition temperature of 10 to 120 ° C.   The floor decorative sheet according to any one of claims 1 to 5, further comprising a primer layer between the first surface protective layer and the second surface protective layer.   A floor decorative material obtained by bonding the base sheet side of the decorative sheet for floor according to any one of claims 1 to 6 to an adherend.