Technical field
[0001]
　The present invention relates to a decorative sheet, and veneer.
BACKGROUND
[0002]
　A method of forming a surface protective layer of the sheet from the cured coating film of an ionizing radiation curable resin to improve the abrasion resistance of the decorative sheet used for the surface material or the like of the building materials are known. However, not at all being scratched even floor decorative sheet scratch resistance is superior in such decorative sheet, scratches Doing scratch test under high load conditions there is a problem that stick (Patent Document 1).
[0003]
　Further, a decorative sheet such as a non-residential floor shops well floor in a house, in order to use the floor of the various usage, a further improvement in scratch resistance of the surface protective layer surface of the decorative sheet Nozomu It is rare.
[0004]
　Therefore, in order to further improve the scratch resistance under high load conditions of the decorative sheet, it has been proposed to harden the surface protective layer. However, an excessively hard surface protective layer, the decorative sheet V cutting, when applying the bending lapping etc., occurs a crack or break in the surface protective layer. Thus, in the decorative sheet, to achieve both the hardness for the bending processability and scratch resistance is not always easy.
CITATION
Patent Document
[0005]
Patent Document 1: JP 2005-74683 JP
Summary of the Invention
Problems that the Invention is to Solve
[0006]
　An object of the present invention has excellent scratch resistance under high load conditions, it is to provide a decorative sheet, and decorative plates using the same having excellent bending workability.
Means for Solving the Problems
[0007]
　The present inventors have result of intensive studies to achieve the above objects, it has found that decorative sheet and decorative laminate below can solve the problems of the present invention.
1. The first olefin resin layer, the second olefin resin layer, and the decorative sheet having a surface protective layer in this order,
　the second olefin resin layer indentation hardness H of IT 2 of the surface protective layer indentation hardness H IT 1 ; and the following formulas (1) and　
　(2) H iT 2　≧ 100 MPa (1)
H　iT 1 > H iT　　　　 　2 (2) decorative sheet characterized by satisfying. 2. Indentation hardness H of the surface protective layer IT 1 is the following formula 　(3); 450 MPa> H IT 1　　(3) meet, decorative sheet according to item 1. 3. Indentation hardness H of the second olefin resin layer

IT 2 and indentation hardness H of the first olefin resin layer IT 3 and the following formula (4);
　H IT 2 > H IT　　　 　　3 (4) meet, decorative sheet according to 1 or 2. 4. The second olefin resin layer is microcrystalline olefin resin layer, the decorative sheet according to any one of claim 1-3. 5. The surface protective layer contains the following inorganic fine particles having a mean particle size of 10 [mu] m, the decorative sheet according to any one of claim 1-4. 6. In order in the thickness direction, and the decorative board base material, veneer consists laminate and a decorative sheet according to any one of items 1-5.

The invention's effect
[0008]
　According to the present invention is excellent in abrasion resistance under high load conditions, it is possible to obtain a decorative sheet, and decorative plates using the same having excellent bending workability.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009]
Is a schematic view showing a cross section of one embodiment of the decorative sheet of FIG. 1 the present invention.
It is a schematic view showing another embodiment of the cross-section of the decorative sheet of the present invention; FIG.
3 is a schematic view of a cross section of the decorative sheet and a combination of a decorative board substrate showing the formation of a decorative board of the present invention.
4 is a diagram for explaining a method of measuring indentation hardness in the present specification.
DESCRIPTION OF THE INVENTION
[0010]
　1. Decorative sheet
　will be described below in detail decorative sheet and decorative laminate of the present invention.
[0011]
　Figure 1 is a schematic diagram illustrating a decorative sheet One embodiment of the cross-section of the present invention, in the thickness direction, the first olefin resin layer 3, the decorative with the second olefin resin layer 2, and a surface protective layer 1 in this order sheet 10 is illustrated. Further, in FIG. 2, embossed recess 4 is formed from at least a surface protective layer side. It will be described below with reference to the accompanying drawings.
[0012]
　In this specification, taking the Figure 1 as an example, the direction in which the surface protective layer 1 as viewed from the second olefin resin layer 2 is laminated referred to as "upper" or "front surface", the second olefin resin the direction in which the first olefin resin layer 3 when viewed from the layer 2 are laminated referred to as "below" or "back". Then, the decorative sheet or decorative plate and "surface of the surface protective layer (side)", "table surface of the (side)" or refers to a surface that is visible after installation of the decorative sheet or decorative plate.
[0013]
　The numerical range indicated by "-" herein means "above", "below". For example, notation α ~ βmm means less than αmm βmm.
(Decorative sheet)
　decorative sheet 10 of the present invention, the first olefin resin layer 3 as shown in FIG. 1, the second olefin resin layer 2, and a surface protective layer 1 A decorative sheet having in this order,
　the second olefin hardness indentation of the resin layer 2 is H iT 2 indentation hardness H of the surface protective layer 1 iT 1 and the following formulas (1) and
　(2); H iT 2　≧ 100 MPa (1)
H　iT 1 > H iT 2　　　　　 (2) and satisfies the. (Indentation hardness) 　herein, "indentation hardness" of each layer, nano measured using a surface film physical property tester tri Boyne indenter (R) "TI-950" (Hysitron Inc.) indicated by indentation hardness.

[0014]
　Incidentally, Tri Boyne indenters (registered trademark) "TI-950" each layer of indentation hardness using (H IT Measurement method)
(1) with reference to FIGS. 4 (a) to Berkovich indenter shown, FIG push the Berkovich indenter in the measurement sample, as shown in (b) at below the pushing condition, triangular pyramid geometry that could be on the surface from shape, "contact projected area corrected with device standard methods (Ap) (mm 2 calculates a)", the maximum test load (F max determine the hardness by dividing)
[0015]
That, H IT = F max is / Ap.
(2) where indentation conditions for the first olefin resin layer and the second olefin resin layer, at room temperature (laboratory ambient temperature), as shown in FIG. 4 (c), first 0-loads up 50μN was added at 5 seconds (i.e. 10μN / s), then 50MyuN (F max hold) 5 seconds at a load of performing finally unloading until 50 ~ 0μN in 10 seconds. As for the surface protective layer, first apply a load of up to 0 ~ 100 N for 10 seconds (i.e. 10μN / s), then 100 N (F max hold a load of) 5 seconds, removing the last to 100 ~ 0μN load is carried out for 10 seconds. Usually, since the push amount (h) is about 100 ~ 150 nm, the push-in direction of the thickness of the sample layer may be a more 1.0 .mu.m (preferably 1.5μm or more).
[0016]
　Ap is 24.50 [h max -epsilon (h max -h r )] 2 with the calculated (here, epsilon is a correction coefficient according to the geometry of the indenter, h r the surface after unloading the remaining three are pyramidal geometry is the depth.).
(3) In addition, when the hardness measurements, measuring the hardness of the cross-section of the layer to be measured in order to avoid the hardness effect of the layers other than the layer serving as the measurement sample. That is, the decorative sheet was embedded in a resin (cold curing type epoxy two-component curing resin), after curing by standing for at least 24 hours at room temperature, the layer to be measured for embedding samples cured by mechanical polishing sectional expose the, the cross-sectional hardness of the cross section of each layer by the Berkovich indenter pushing it in (position avoiding the fine particles when the fine particles such as fillers contained in the layer) of the layer to be measured taking measurement.
(4) for each layer, respectively measured indentation hardness of 10 points so as not to cause deviation, "indentation hardness H of the surface protective layer respectively an average value of 10 points IT 1 ", "second olefin resin indentation hardness of the layer H IT 2 "and" indentation hardness H of the first olefin resin layer IT 3 to ".
[0017]
　In the present invention, the second olefin resin layer indentation hardness H of IT 2 indentation hardness H of the surface protective layer IT 1 and is required to satisfy the following formula (1) and (2). Can not be obtained and excellent scratch resistance and bending workability under high load conditions when the indentation hardness of the second olefin resin layer and the surface protective layer does not satisfy the following formula (1) and (2) .
[0018]
　H IT 2　≧ 100 MPa (1)
H　IT 1 > H IT　　　 　　2 (2) 　In addition, indentation hardness H of the surface protective layer IT 1 is the reason that exert the scratch resistance at relatively high load in two indentation hardness H of the olefin resin layer iT 2 must be greater than a and 100MPa exceeded.
[0019]
　Further, from the viewpoint of obtaining excellent abrasion resistance and good bending workability, indentation hardness H of the surface protective layer IT 1 represented by the following formula
　(3); 450 MPa> H IT 1　　(3)
preferably satisfies .
[0020]
　Also, excellent from the viewpoint of obtaining scratch resistance and good bending workability, indentation hardness H of the second olefin resin layer IT 2 and indentation hardness H of the first olefin resin layer IT 3 and is represented by the following formula (4);
　H iT 2 > H iT　　　　　3 (4) is preferably satisfied. (First olefin resin layer) 　The first olefin resin layer is a layer formed from an olefin resin, as the olefinic resins, such as ethylene, propylene, homopolymers of olefins butene, ethylene - block copolymer of propylene a random copolymer; and at least one of ethylene and propylene, butene, pentene, copolymers of at least one other olefin hexene and the like; and at least one of ethylene and propylene, vinyl acetate, at least one vinyl alcohol copolymers with other monomers; and the like. Among them, from the viewpoint of obtaining a good scratch resistance and good bending workability, polyethylene, polypropylene are preferred, particularly polyethylene.

[0021]
　Polyethylene may be a homopolymer of ethylene, ethylene, ethylene can be copolymerized with other comonomers (e.g., propylene, 1-butene, 1-hexene, and 1-octene α- olefins, acetic acid vinyl, or a copolymer of vinyl alcohol and the like). The polyethylene resin, for example, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultra high molecular weight polyethylene ( UHMWPE), polyethylene (PEX), and the like crosslinking. These polyethylenes may be used singly or in combination of two or more thereof.
[0022]
　Polypropylene may be a homopolymer of propylene, propylene, propylene and other copolymerizable comonomers (e.g., ethylene, 1-butene, 1-hexene, and 1-octene α- olefin; acetate vinyl, or a copolymer of vinyl alcohol and the like). These polypropylene may be used alone or in combination of two or more thereof.
[0023]
　Indentation hardness H of the first olefin resin layer IT 3 and indentation hardness H of the second olefin layer IT 2 and preferably has a relationship of formula (4).
[0024]
　Among them, from the viewpoint of obtaining a good scratch resistance and good bending workability, indentation hardness H of the first olefin resin layer IT 3 it is preferably 10 ~ 80 MPa, a 15 ~ 70 MPa it is more preferable, more preferably from 20 ~ 60 MPa, and particularly preferably 30 ~ 55 MPa. By being within this range, in addition to scratch resistance and impact resistance of the decorative sheet (particularly耐凹viewed properties) can be maintained satisfactorily, first with tension applied during printing when performing printing and coating on a printing press it is possible to prevent the olefin resin layer will extend. Further, bending easily suppress cracking and breaking of the surface protective layer in the processing, impact resistance (particularly crack resistance) can be maintained satisfactorily.
[0025]
　Incidentally, indentation hardness can be set appropriately, such as by mixing the elastomer or resin by mixing two or more resins having different hardness.
[0026]
　The thickness of the first olefin resin layer, from the viewpoint of bending workability and excellent abrasion resistance, preferably from 30 ~ 120 [mu] m, more preferably 40 ~ 110 [mu] m, more preferably 50 ~ 100 [mu] m, particularly preferably 55 ~ 85 .mu.m.
[0027]
　Incidentally, the first olefin resin layer in the present specification, the thickness of the second olefin resin layer and the surface protective layer is an average value when measuring thickness of 10 places.
(Second olefin resin layer)
　The second olefin resin layer is a layer formed from an olefin resin, the indentation hardness H IT 2 is a layer necessary to satisfy the above formula (1) and (2).
[0028]
　The olefin resin forming the second olefin resin layer, the same thing can be exemplified an olefin resin which can form a first olefin resin layer. Among them, in view of bending workability and excellent scratch resistance, polyethylene, polypropylene is preferred, particularly polypropylene are preferred.
[0029]
　Polypropylene may be a homopolymer of propylene, propylene, propylene and other copolymerizable comonomers (e.g., ethylene, 1-butene, 1-hexene, and 1-octene α- olefin; acetate vinyl, or a copolymer of vinyl alcohol and the like). These polypropylene may be used alone or in combination of two or more thereof. In the present invention, the excellent scratch resistance and bending workability viewpoint, it is particularly preferably a propylene homopolymer (homopolypropylene).
[0030]
　The second olefin resin layer, the indentation hardness H IT 2 for, be required to satisfy the following formula (1) and (2), preferably satisfy the following formula (4).
[0031]
　H IT 2　≧ 100 MPa (1)
H　IT 1 > H　　　　 　IT 　2 　(2) H IT 2 > H IT　　　 　　3 (4) 　indentation hardness H of the second olefin resin layer IT 2 is abrasion resistance and bending workability from the viewpoint balance of, preferably not less than 200MPa or less 100 MPa, more preferably at least 150MPa or less 105 MPa, more preferably above 110 MPa 130 MPa or less.

[0032]
　H IT 2 When less than 100 MPa, scratch resistance and impact resistance or poor (especially耐凹viewed properties), in the tension applied during printing elongation second olefin resin layer when performing the printing or coating on a printing press it may be put away. If it exceeds 200 MPa, it may bend to occur cracks and fractures in the surface protective layer and the impact resistance in the processing (in particular the crack resistance) resulting in inferior.
[0033]
　Indentation hardness H 2 To adjust easily, for example, mixing two or more resins having different hardness, mixing the elastomer resin, the second olefin resin layer Microcrystalline olefins it can be set appropriately, such as by a resin layer.
[0034]
　To obtain microcrystals olefin resin layer, for example, can be carried out by by incorporating a crystal nucleating agent to the olefin resin composition for forming the second olefin resin layer melted, then cooled. In this case, as a cooling method, for example, cooling by contacting the material extruded from the die to the cooling roll (chill roll) through the cooling water at the time of extrusion molding chill roll method in which the cooling.
[0035]
　The crystal nucleating agent, such as fatty acid metal salts, metal salts of phosphonic acids, phosphoric acid ester metal salts, benzoic acid metal salt, pimelic acid metal salts, metal salt-based nucleating agent such as rosin metal salts; fatty acid esters, fatty amides, benzylidene sorbitol, quinacridone, organic crystal nucleating agents such as cyanine blue; inorganic nucleating agent such as talc; and the like.
[0036]
　As the crystal nucleating agent can also be used as the above-mentioned crystal nucleating agent is contained in nanoshells. The use of encapsulated crystalline nucleating agent nanoshells, the crystal nucleating agent in the second olefin resin layer is more uniformly dispersed, melting conditions, regardless of the conditions such as the cooling conditions, easily and stably , indentation hardness H iT 2 can be adjusted, also the excellent scratch resistance and good bending workability can be obtained.
[0037]
　In the present invention, the term "nanoshells", "it has a shell-like a closed film structure nano-sized, hollow vesicles" is, preferably less than 380 nm, more preferably have an average primary particle size of less 375nm It means a thing. Here, the average primary particle diameter, a transmission electron microscope (TEM), a value calculated by statistical processing from the observation image was measured by a scanning transmission electron microscope (STEM). Calculated by statistical processing, specifically, about 1000 particles randomly selected from the SEM image, measuring the diameter, when creating a histogram of 3nm division, performed by calculation using the following formula (A) those were. The number average primary particle diameter D obtained in the formula (A) np were an average primary particle diameter of this specification.
[0038]
　D np = .SIGMA.n i d i / .SIGMA.n i (A)
D np : The number-average molecular weight
　　　d i : Histogram of the i th diameter
　　　n i : the frequency
　in the present invention, the average primary particle diameter of nanoshells, the visible light wavelength region ( is 380 ~ 750 nm) less than, or a degree less than half of the wavelength of visible light, i.e., is preferably less than 380 nm, more specifically, preferably less than 1 nm 380 nm, 1 ~ 375 nm Gayori , more preferably from 5 ~ 300 nm, more preferably more that 10 ~ 250 nm, particularly preferably 15 ~ 200 nm. When the average primary particle size is within the above range, more easily adjust the indentation hardness of the second olefin resin layer, it is possible to obtain the bending workability and good scratch resistance.
[0039]
　The nanoshells is not particularly limited as long as it can containing the aforementioned crystal nucleating agent, may be a single layer film, it may be a multilamellar, and smaller average primary particle size , to improve the dispersibility of the crystal nucleating agent, from the viewpoint of improving the excellent scratch resistance and bending workability more efficiently, preferably a single layer film. The material for forming the nanoshells, more easily adjust the indentation hardness of the second olefin resin layer, from the viewpoint of obtaining excellent abrasion resistance and bending workability, phospholipids are preferred.
[0040]
　In the present invention, the form of the nanoshells, more preferably a single layer film made of phospholipids. With nanoshells consisting of phospholipids, to improve compatibility with the resin forming the second olefin resin layer described above, to adjust the indentation hardness of the second olefin resin layer, excellent scratch resistance and in order to increase the bending workability is advantageous. In addition, by nanoshells is a single layer film, the average primary particle size becomes smaller, the synergistic effect of the dispersibility improvement by phospholipids forming the nanoshells, improves the dispersibility of the crystal nucleating agent, more efficiently adjust the indentation hardness of the second olefin resin layer, it is possible to obtain a superior abrasion resistance and bending workability.
[0041]
　The phospholipids, such as phosphatidylcholine, phosphatidyl diethanolamine, phosphatidylserine, phosphatidic acid, phosphatidyl glyceryl roll, phosphatidylinositol, Karujiopin, egg yolk lecithin, water 添黄 egg lecithin, soy lecithin, glycerophospholipids such as hydrogenated soybean lecithin; sphingomyelin, ceramide phosphoryl ethanolamine, sphingophospholipids such as ceramide phosphoryl glycerol; and the like. These phospholipids may be used alone or in combination of two or more.
[0042]
　As a method of containing the above-mentioned crystal nucleating agent nanoshells, e.g., Bangham method, an extrusion method, hydration method, detergent dialysis method, reverse phase evaporation method, freeze-thaw method, supercritical reverse phase evaporation method, and the like and the like.
[0043]
　Here, Bangham method, chloroform, a solvent such as methanol, were added and dissolved into the phospholipid to form a thin film made of phospholipids by removing the solvent using an evaporator, after addition of the crystal nucleating agent , using a mixer, for example, by stirring at high speed of about 1000 ~ 2500 rpm, hydrated, dispersed, a method of containing the crystal nucleating agent to nanoshells. An extrusion method is a method of passing the filter in place of the mixer used as an external perturbation. Hydration methods, in Bangham method, without using a mixer, gently stirred, and dispersed, a method of containing the crystal nucleating agent to nanoshells. Reverse-phase evaporation method can be prepared by dissolving the phospholipid diethyl ether, the solvent such as chloroform, making the W / O emulsion by adding the crystal nucleating agent (or may be obtained by the state of dispersion.), Vacuum from the emulsion the solvent was removed in the lower, water was added, a method of containing the crystal nucleating agent to nanoshells. Also, freeze-thaw method, cooling as external perturbations is at least a method of performing any one of heating, cooling, a method of containing the crystal nucleating agent nanoshells by repeated heating.
[0044]
　In addition, by adopting the supercritical reverse phase evaporation method, more reliable, and easily, the nanoshells can be a single layer film made of phospholipids. Supercritical reverse phase evaporation method, a supercritical state, or critical point or higher temperature conditions, or by using a carbon dioxide pressure conditions, a method of containing the crystal nucleating agent to nanoshells. Here, supercritical carbon dioxide, the critical temperature (30.98 ° C.) and critical pressure (7.3773 ± 0.0030MPa) above means a carbon dioxide in a supercritical state, a temperature of more than the critical point lower, or a carbon dioxide pressure conditions, only one of the temperature or critical means of carbon dioxide under conditions above the critical condition.
[0045]
　Supercritical reverse phase evaporation method, specifically, the above crystal nucleating agent, and the supercritical carbon dioxide, water was added to a mixture of phospholipids, by stirring, an emulsion of supercritical carbon dioxide and water phase is formed and then, carbon dioxide is expanded under a reduced pressure, phase inversion occurs to evaporate, the surface of the crystal nucleating agent to form a nanoshell covered with a single layer film of phospholipids, crystal nuclei are contained in nanoshells agent obtain, is that. Incidentally, as in the conventional, if it is desired to form a multi-layer, in the above method, the crystal nucleating agent, and phospholipid, a mixture of water, may be added to the supercritical carbon dioxide.
[0046]
　In the present invention, nanoshells, materials other than phospholipids, for example, aliphatic polyhydric carboxylic acids, polycarboxylic acid alkyl amine, poly (meth) molecular weight from 10,000 to 500,000, such as acrylic acid, preferably 15,000 to 300,000, more preferably 20,000 to 200,000 approximately polymeric surfactants; lauric acid, myristic acid, stearic acid, behenic acid, montanic acid, preferably 10 to 30 carbon atoms such as ricinoleic acid, more preferably 12 saturated or unsaturated fatty acids to 28, lithium, sodium, potassium, magnesium, calcium, barium, zinc, fatty acid metal salt is a metal such as aluminum bonded; (meth) acryloxy propyl triethoxysilane, (meth) acryloxy propyl trimethoxy silane (meth) acryloxy-based silane coupling agent, vinyl tri Tokishishiran, vinyl silane coupling agents such as vinyltrimethoxysilane, (epoxycyclohexyl) ethyltrimethoxysilane, epoxy-based silane coupling agents such as glycidoxypropyltrimethoxysilane, isocyanate silane such as isocyanate propyl triethoxysilane coupling agent, a silane coupling agent such as a phenyl-based silane coupling agent such as phenyltrimethoxysilane; tetrakis [bis (allyloxymethyl) butoxy] titanium, dipropoxy titanium Geo Seo stearate, (butoxycarbonyl benzoyloxy) tri butoxy, triisostearate isopropyl titanium, dibutoxy - bis (triethanolaminato) titanium, tetrakis (ethylhexyl oxy) titanium, dipropoxy - Scan titanate coupling agent such as (acetylacetonato) titanium; dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, cyclic dimethyl silicone oil, alkyl-modified silicone oil, long-chain alkyl-modified silicone oil, higher fatty acid-modified silicone silicone oils such as oil; polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wa Box, microcrystalline wax, paraffin wax, Fischer-Tropsch waxes, hydrocarbon waxes such as Sasol wax, preferably an ester wax of an aliphatic carboxylic acid and dipentaerythritol to 30, more preferably from 12 to 24 10 carbon atoms , carnauba wax, waxes such as deoxidized waxes such as montan wax; consist dispersant such as; polyolefin resin maleic acid, sulfonic acid, carboxylic acid, modified resin modified with an organic acid such as rosin acid it may be. These dispersants may be used alone or in combination of two or more.
[0047]
　As an example of a method for manufacturing encapsulated crystalline nucleating agent nanoshells, phosphoric acid ester metal salt-based nucleating agent as a crystal nucleating agent (2,2'-methylenebis - (4,6-di -tert- butylphenyl) phosphate taking the case of using sodium) is described more specifically.
[0048]
　The organic solvent 100 parts by weight as methanol, the phosphoric acid ester metal salt-based nucleating agent 60 to 100 parts by weight nucleating agent, and phosphatidylcholine 2-10 parts by weight phospholipids and kept 40 ~ 70 ° C. container sealed put in, the internal pressure by supplying carbon dioxide to a supercritical state in the vessel so that 7.5 ~ 25 MPa. Then, the inside of the vessel was stirred at a high speed of about 1000 ~ 2500 rpm, supplying ion exchange water 50 to 150 parts by weight. While the temperature and pressure are maintained such that the supercritical state, after stirring was continued for about 10 to 25 minutes, and discharged carbon dioxide from the container, by returning the vessel to atmospheric pressure, a single consisting of phospholipids was included in layer film nanoshells can be fabricated crystal nucleating agent (phosphoric acid ester metal salt-based nucleating agent). Average primary particle diameter of the obtained crystal nucleating agent is contained in nanoshells is about 10 ~ 250 nm.
[0049]
　The content of the nucleating agent in the second olefin resin layer, with respect to 100 parts by mass of the resin component forming the second olefin resin layer is preferably 0.01 to 5 parts by weight, more from 0.02 to 3 parts by weight preferably, further preferably 0.03 to 1 part by mass, particularly preferably 0.05 to 0.5 part by weight. When the content of the crystal nucleating agent is within the above range, it is easy to uniformly disperse in the resin to form a second olefin resin layer, the effect as the crystal nucleating agent is easily obtained easily and stably indentation hardness H iT 2 can be adjusted, also the excellent scratch resistance and bending workability can be obtained.
[0050]
　The thickness of the second olefin resin layer, from the viewpoint of obtaining a bending property and excellent abrasion resistance, preferably from 30 ~ 120 [mu] m, more preferably 40 ~ 110 [mu] m, more preferably 50 ~ 100 [mu] m, particularly 55 ~ 85 .mu.m preferable. If it is less than 30 [mu] m, scratch resistance and impact resistance or poor (especially耐凹seen property), there is a possibility that the second olefin resin layer in tension resulting in elongation applied during printing when performing printing and coating on a printing press . If it exceeds 120 [mu] m, there is a bending possibility that occur cracks and fractures and impact resistance (particularly resistance to cracking) resulting in poor surface protective layer in the processing.
(Surface protective layer)
　surface protective layer, as shown in Figures 1 and 2, a layer exposed to the outer surface provided on the outermost surface of the decorative sheet, stain resistance of the decorative sheet, scratch resistance, chemical It is provided to improve the surface properties of the sex and the like. The surface protective layer, the indentation hardness H IT 1 is required to satisfy the following formula (2).
[0051]
　H IT 1　> H IT 2　　　　 　(2)
　indentation hardness H of the surface protective layer IT 1 is the reason that exert the scratch resistance at relatively high load in the second olefin resin layer indentation hardness H IT 2 must be greater than a and 100MPa exceeded.
[0052]
　Incidentally, indentation hardness can be set appropriately, such as by mixing the elastomer or resin by mixing two or more resins having different hardness.
[0053]
　From the viewpoint of abrasion resistance, indentation hardness H IT 1 is preferably at least 170 MPa, more preferably at least 250 MPa, more preferably not less than 300 MPa, not less than 350MPa even more preferably from.
[0054]
　Moreover, the bending workability viewpoint, indentation hardness H IT 1 preferably satisfies the following formula (3) or less, more preferably 400 MPa or less, more preferably 350 MPa or less, and even more preferably from 320 MPa.
[0055]
　450 MPa> H IT 1　　(3)
　In addition, indentation hardness H described above IT 1 preferred range of multi-step upper and lower limits of the may be combined. For example a lower maximum value, the maximum value and the H in combination of upper IT 1 the scope of can be less than or more 350 MPa 450 MPa.
[0056]
　Surface protective layer, stain resistance of the decorative sheet, scratch resistance, to improve the surface properties such as chemical resistance, from the viewpoint of satisfying the indentation hardness of the above, made of a cured product of the curable resin composition preferably, the curable resin composition, for example, to obtain a thermosetting resin, two-component curing resin, a resin composition comprising a curable resin such as an ionizing radiation-curable resins. better surface properties terms, two-part curable resin, the resin composition comprising an ionizing radiation-curable resin is preferable as the curable resin.
[0057]
　The two-part curable resin is not particularly limited as long as it is a resin cured by the base and curing agent, preferably a main agent and a polyol (polyhydric alcohol), 2-component curing urethane which the curing agent and an isocyanate curing agent resins.
[0058]
　The main agent, for example, polyethylene glycol, polypropylene glycol, butylene glycol, neopentyl glycol, polyols such as 1,6-hexanediol, acrylic polyols, polyester polyols, polyols having a hydroxyl group as a functional group such as polyether polyols, etc. preferably it is mentioned. These can be used alone or in combination of plural kinds.
[0059]
　As the isocyanate curing agent may appropriately be used conventionally known compounds, for example, 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), aromatic isocyanates such as naphthalene diisocyanate; 1,6 hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), aliphatic, such as hydrogenated tolylene diisocyanate (or alicyclic) isocyanates; polyisocyanates such as are used. Further, adducts or multimers of these various isocyanates such as an adduct of tolylene diisocyanate, etc. tolylene diisocyanate trimer (trimer) is also used.
[0060]
　Ionizing radiation-curable resin, among the ionizing radiation, i.e. electromagnetic waves or charged particle beams, those having energy quantum capable of polymerizing or crosslinking the molecules, e.g., other ultraviolet (UV) or electron beam (EB), X-ray, electromagnetic waves such as γ-rays, alpha rays, a resin which is cured by irradiating a charged particle beam of the ion beam or the like. Specifically, as the ionizing radiation curable resin, conventionally it has been and polymerizable monomer can be suitably selected from polymerizable oligomers and prepolymers.
[0061]
　The polymerizable monomer has a radically polymerizable unsaturated groups in the molecule (meth) acrylate monomers are preferred, inter alia polyfunctional (meth) acrylate monomers are preferred. Examples of the polyfunctional (meth) acrylate monomer having two or more ethylenically unsaturated bonds in the molecule (meth) may be any acrylate monomer, e.g., diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate preferably. These (meth) acrylate monomers may be used alone or in combination of two or more.
[0062]
　The polymerizable oligomer, oligomer having a radical polymerizable unsaturated group in the molecule, for example, urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, acrylic (meth) acrylates such as oligomeric (meth) acrylate oligomer is preferably cited. These polymerizable oligomer may be used alone or in combination of two or more.
[0063]
　Curable resin composition, in addition to the above-mentioned curable resin may contain a dispersing agent to be described later.
[0064]
　Further, the curable resin composition, as additives within a range not to impair the object of the present invention, an ultraviolet absorber, an ultraviolet screening agent, a light stabilizer, abrasion resistance enhancing agents, polymerization inhibitors, crosslinking agents, infrared absorbing agents, antistatic agents, adhesion improving agents, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, antiblocking agents, lubricants, may be added to the solvent or the like. Among them, for improving weather resistance, ultraviolet absorber preferably contains a weathering agent such as a light stabilizer.
[0065]
　As the ultraviolet absorber include benzophenone, benzotriazole, triazine, salicylate, acrylonitrile and the like, as the light stabilizer, hindered amine, acrylate, oxamide-based, and cyanoacrylate or the like .
[0066]
　Surface protective layer may contain a dispersing agent.
[0067]
　As the dispersing agent, exemplified as the material capable of forming the above nanoshells, polymeric surfactants, fatty acid metal salt, a silane coupling agent, titanate coupling agent, silicone oil, waxes, modified resins. These dispersants may be used alone or in combination of two or more.
[0068]
　Further, as a dispersing agent, a dispersing agent to be encapsulated in the nanoshells may be used. Nanoshells in dispersing agent to be encapsulated in nanoshells may be the same nanoshells the crystal nucleating agent to be encapsulated in the nanoshells in the second olefin resin layer, and a method for manufacturing a crystal nucleating agent for its manufacturing method are also included in the nanoshells it is the same.
[0069]
　A dispersing agent to be encapsulated in nanoshells, by containing the inorganic fine particles to be described later, can easily increase the indentation hardness.
[0070]
　As an example of a method for manufacturing encapsulated dispersant to nanoshells, more specifically described as an example a case of using a methacryloxypropyl trimethoxysilane as a dispersant.
[0071]
　The organic solvent 100 parts by weight as methanol, methacryloxypropyl trimethoxy silane 40-80 parts by weight as a dispersant, and a phosphatidylcholine 2-10 parts by weight phospholipid, and sealed in a container kept at 40 ~ 70 ° C. , the internal pressure by supplying carbon dioxide to a supercritical state in the vessel so that 7.5 ~ 25 MPa. Then, the inside of the vessel was stirred at a high speed of about 1000 ~ 2500 rpm, supplying ion exchange water 50 to 150 parts by weight. While the temperature and pressure are maintained such that the supercritical state, after stirring was continued for about 10 to 25 minutes, and discharged carbon dioxide from the container, by returning the vessel to atmospheric pressure, a single consisting of phospholipids was included in layer film nanoshells can be manufactured dispersant (methacryloxypropyl trimethoxysilane).
[0072]
　The average primary particle diameter of the thus dispersing agent to be encapsulated in the resulting nanoshells, like the average primary particle size of the dispersed agent to be encapsulated to the nanoshells is preferably less than 380 nm, more specifically is less than 380nm is preferably at least 1 nm, more preferably 1 ~ 375 nm, more preferably 5 ~ 300 nm, even more preferably 10 ~ 250 nm, particularly preferably 15 ~ 200 nm.
[0073]
　The content of the dispersant with respect to 100 parts by mass of the resin component forming the surface protective layer is preferably from 0.01 to 30 parts by weight, more preferably from 0.05 to 15 parts by weight, 0.1 to 10 parts by weight but more preferably, in particular 0.3 to 5 parts by weight is preferred.
[0074]
　Surface protective layer further from the viewpoint of improving the scratch resistance, preferably contains inorganic fine particles. Examples of the inorganic fine particles, silica, alumina, aluminosilicates, kaolinite, calcium carbonate, barium sulfate and glass.
[0075]
　The average particle diameter of the inorganic fine particles is not critical, is preferably 20 [mu] m or less, 1 ~ 20 [mu] m is preferably Among them, 2 ~ 15 [mu] m is more preferable.
[0076]
　The average particle diameter of the inorganic fine particles, the particles in the solution was measured by a dynamic light scattering method, the 50% particle diameter when representing the particle size distribution by volume cumulative distribution: a (d50 median diameter). 50% particle size, for example, can be measured using a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.).
[0077]
　The content of the inorganic fine particles with respect to 100 parts by mass of the resin component forming the surface protective layer is preferably 1 to 30 parts by weight, more preferably from 2 to 25 parts by weight, more preferably 5 to 20 parts by weight.
[0078]
　The thickness of the surface protective layer is preferably 3 ~ 45 [mu] m, more preferably 5 ~ 35 [mu] m, more preferably 10 ~ 30 [mu] m. If the thickness of the surface protective layer is within the above range, excellent surface properties by the combination of the first olefin resin layer and the second olefin resin layer described above can be obtained.
(Other Layers)
　The decorative sheet of the present invention, the first olefin resin layer of the above, other second olefin resin layer and the surface protective layer, depending on the application, for example, decorative layer, a primer layer, an adhesive layer, etc. it can have.
(Decorative layer)
　decorative sheet of the present invention, from the viewpoint of improving the design property can have a decorative layer. Decorative layer, for example, between a first olefin resin layer and the second olefin resin layer, or between the second olefin resin layer and the surface protective layer may be provided on the surface protective layer choice.
[0079]
　Decorative layer, for example, a colored layer that covers the entire surface may be a (so-called solid colored layer), even pattern layer formed by the various patterns is printed using an ink and printing machine it may, or may be a combination of these. Furthermore, the decorative layer may be provided at a plurality of locations in the same layer, it may be provided in a plurality of layers as well as more.
[0080]
　For example, in the case of colored concealing the background color of the decorative board base material, by a solid colored layer, while colored hiding, it is possible to improve the design. From the viewpoint of further improving the design property, it may be combined with the solid colored layer and the picture layer, whereas, when to utilize the base pattern of the decorative board base material, by providing the pattern layer only without the solid colored layer good.
[0081]
　The ink used for the decorative layer, the binder to the pigment, colorant such as a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, used those light stabilizers such as a suitable mixture It is.
[0082]
　There are no particular limitations on the binder, for example, urethane resins, acryl polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane - acrylic copolymer, polycarbonate-based urethane - acrylate copolymer (polymer main chain has a carbonate bond, terminated, polymers having two or more hydroxyl groups in the side chain (polycarbonate polyol) derived from the urethane - acrylate copolymer), vinyl chloride - vinyl acetate copolymer resin, vinyl chloride - acetate vinyl - acrylic copolymer resin, chlorinated polypropylene resin, nitrocellulose resin, resins such as cellulose acetate resins preferred. These binders may be used alone or in combination.
[0083]
　As the colorant, the background color of the decorative board base material is colored hiding, and from the viewpoint of improving the design property, for example, white pigments, iron black, chrome yellow, titanium yellow, red iron, cadmium red, ultramarine blue, cobalt blue inorganic pigments and the like; scaly foil titanium dioxide-coated mica, basic lead carbonate and the like; quinacridone red, isoindolinone yellow, organic pigments or dyes such as phthalocyanine blue; aluminum, metal pigments consisting of scale-like foil pieces such as brass it is also possible to use colorants such as pearlescent (pearl) pigments consisting of migraine.
[0084]
　If you are having a pattern layer as a decorative layer, as are the patterns, wood grain patterns, marble (e.g. travertine marble) or the like of the pebbled pattern imitating the surface of the rock, fabric patterns imitating a weft or cloth-like pattern, tile lamination pattern, there is a brick product pattern or the like, there are these the parquet in complex, also pattern such as patchwork. These patterns are usually yellow, red, also formed by the blue, and besides by the black process color is formed by multi-color printing, multi-color printing by spot performed to prepare a plate of individual colors constituting the patterns It is.
[0085]
　The thickness of the decorative layer may be suitably selected according to the desired pattern, the background color of the decorative board base material is colored hiding, and from the viewpoint of improving the design property, preferably 0.5 ~ 20 [mu] m, 1 more preferably ~ 10μm, 2 ~ 5μm is more preferable.
(Primer layer)
　The primer layer is a layer provided in order to mainly improve the adhesion of each layer.
[0086]
　In the decorative sheet of the present invention, a primer layer, for example, it may be provided one or both sides of the first olefin resin layer, one side or both sides of the second olefin resin layer, the like. Similarly to the primer layer, to improve the layers of adhesion, the first olefin resin layer, on one or both surfaces of the second olefin resin layer, oxidation, physical surface treatment such as roughening method, or a chemical it may be subjected to surface treatment of the surface treatment or the like.
[0087]
　The primer layer formed, for example, the illustrated binder as the binder which can be used in the above decorative layer, solvents, stabilizers, plasticizers, catalysts, curing agents, ultraviolet absorbers, a resin composition was a light stabilizer such as a suitable mixture can do.
[0088]
　The thickness of the primer layer, from the viewpoint of improving the adhesion, preferably 0.2 ~ 10 [mu] m, more preferably from 0.5μm ~ 8μm, 1 ~ 5μm are more preferred.
(Synthetic resin backer layer)
　decorative sheet of the present invention, the bottom layer of the decorative sheet, i.e. may comprise a synthetic resin backer layer on the first olefin resin layer side of the decorative sheet. By providing the synthetic resin backer layer, the impact resistance of the decorative material is further improved.
[0089]
　As the resin constituting the synthetic resin backer layer, for example, polypropylene, ethylene - vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, high heat resistance polyalkylene terephthalates [e.g., a portion of ethylene glycol 1 , polyethylene terephthalate was replaced with 4-cyclohexanedimethanol or diethylene glycol, a so-called trade name PET-G (manufactured by Eastman Chemical Company)], polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate - isophthalate copolymer, polycarbonate, polyarylate, polyimide, polystyrene, polyamide, ABS and the like. These resins may be used singly or two or more.
[0090]
　The thickness of the synthetic resin backer layer is preferably 0.1 ~ 0.6 mm, more preferably from 0.15 ~ 0.45 mm, more preferably 0.20 ~ 0.40 mm. By the lower limit of the thickness of the synthetic resin backer layer is in the above range, the impact resistance of the decorative sheet is further improved. The upper limit of the thickness of the synthetic resin backer layer by an above-mentioned range, the warpage of the decorative sheet is further suppressed.
(Concave)
　decorative sheet of the present invention, the recess in the surface protective layer side (e.g., embossed recesses) may have. By having a recess, luxury associated with improvement in the texture of the decorative sheet (touch) is obtained, the design is improved.
[0091]
　Recess has only to present at least the surface protective layer of the decorative sheet of the present invention, may be one depth of the recess remains in the surface protective layer, also those that lead to the first olefin resin layer it may be. From the viewpoint of obtaining excellent texture (the touch), as well as stay in the surface protective layer, which leads to a second olefin resin layer, it is preferable that those leading to the first olefin resin layer are combined.
[0092]
　The pattern of the recesses, for example, wood plate conduit groove, slate surface irregularities, the fabric surface texture A, satin, grain, hairline, a ten thousand linear groove or the like. From the viewpoint of improving the design property, a pattern of recesses is preferably a pattern that is tuned with the pattern of the decorative layer. For example, if the pattern layer is grain pattern, select the wood plate conduit groove as a pattern of the recess, and when tuning the grain of wood and the recess of the picture layer, full of texture in a more realistic feeling of luxury decorative sheet can be obtained.
(Cosmetic method for producing a sheet)
　for the method of manufacturing the decorative sheet of the present invention, which is a preferred embodiment as a cosmetic sheet of the present invention, in the thickness direction, the first olefin resin layer, the decorative layer, the second olefin resin layer and a decorative sheet having a surface protective layer in this order as an example, an example of a manufacturing method thereof.
[0093]
　First, prepare a resin composition for forming the first olefin resin layer, to form a film of the first olefin resin layer by a method such as melt extrusion method, on the said first olefin resin layer to form a decorative layer .
[0094]
　Apart from this, by providing a resin composition for forming the second olefin resin layer, to form a film of the second olefin resin layer by a method such as melt extrusion method, on the said second olefin resin layer, uncured layer coated with curable resin composition, heat or ionizing radiation cured by irradiation to form a surface protective layer.
[0095]
　Then, the decorative layer and an adhesive is applied to at least one surface of the second olefin resin layer, decorative layer and by that the second olefin resin layer is stuck so as to face the first olefin resin layer, decorative layer, the second olefin resin layer, and it is possible to produce a decorative sheet having a surface protective layer in this order.
[0096]
　In the above-described manufacturing method, after forming a decorative layer, a resin composition for forming the second olefin resin layer, extruding a second olefin resin layer lamination, dry lamination, wet lamination, and thermal lamination process not through the thermoplastic resin such as an adhesive and / or an acid-modified polyolefin resin is bonded and crimped is formed by laminating, then, on the said second olefin resin layer, coated with a curable resin composition by the cured layer, heating or ionizing radiation to cure by irradiation, also by forming the surface protective layer, the decorative sheet having the first olefin resin layer, the decorative layer, the second olefin resin layer, and a surface protective layer in this order it can be produced.
[0097]
　Decorative layer, the first olefin resin layer, desired color layer ink used for forming the decorative layer is applied on the second olefin resin layer is formed by providing a pattern layer. Coating of the ink, a gravure printing method, a bar coating method, roll coating method, reverse roll coating method, a known method such as comma coating method, preferably carried out by a gravure printing method.
[0098]
　In the formation of the surface protective layer, the coating of the curable resin composition, so that the thickness after curing becomes a predetermined thickness, preferably gravure coating, bar coating, roll coating, reverse roll coating, known like comma coating by the system, more preferably carried out by gravure coating.
[0099]
　When using ionizing radiation resin composition for formation of a surface protective layer, the uncured resin layer formed by coating of the resin composition by the electron beam, the cured product is irradiated with ionizing radiation such as ultraviolet rays, the surface serving as a protective layer. Here, when an electron beam is used as the ionizing radiation, for the acceleration voltage, but may be suitably selected according to the thickness of the resin and the layer to be used, it is possible to cure the uncured resin layer at normal acceleration voltage of 70 to about 300kV preferable.
[0100]
　Irradiation dose is preferably an amount that crosslinking density of the ionizing radiation curable resin is saturated, usually 5 ~ 300kGy (0.5 ~ 30Mrad), it is preferably selected in the range of 10 ~ 50kGy (1 ~ 5Mrad).
[0101]
　The electron beam source is not particularly limited, for example Cockroft Walton type, Van de Graft type, resonance transformer type, insulated core transformer type, or linear type, Dynamitron type, use various electron beam accelerators of the high frequency type, etc. be able to.
[0102]
　In the case of using ultraviolet rays as the ionizing radiation, emits those containing the ultraviolet wavelength 190 ~ 380 nm. There are no particular limitations on the ultraviolet light source, for example a high-pressure mercury lamp, low pressure mercury lamp, a metal halide lamp, carbon arc 燈等 used.
[0103]
　If the formation of the surface protective layer using a thermosetting resin composition, heat treatment is performed in accordance with the resin composition to be used, it may be formed a surface protective layer cured.
[0104]
　In the case of providing a primer layer, a resin composition for forming the primer layer, for example, a gravure printing method, a bar coating method, roll coating method, reverse roll coating, is applied by a known method such as comma coating method it can be formed.
[0105]
　In the case of providing a synthetic resin backer layer, for example, a synthetic resin layer backer layer prepared in such a T-die extrusion method, and a first olefin resin layer is laminated by dry lamination via heat lamination or adhesive etc., it can be formed in a known manner.
[0106]
　In the case of forming a recess, in consideration of the easiness of the work, it is preferable to adopt the embossing. Embossing may be performed by conventional methods using embossing machine known sheet or web offset.
[0107]
　2. Veneer
　decorative laminate of the present invention, in order in the thickness direction, and the decorative plate substrate composed of a laminate comprising a decorative sheet of the present invention described above.
[0108]
　3 shows an example of a (the surface opposite to the veneer bonding the substrate 11 and the surface protective layer side) decorative plate 12 are laminated in this order decorative sheet 10 of the present invention on the decorative board base material 11 .
[0109]
　Although not limited as decorative board substrate, for example, medium density wood fiber board, high-density wood fiber board, particle board, softwood plywood, hardwood plywood, fast Shigeki plywood, cork sheet, cork containing composite substrate, thermoplastic resin plate (polyvinyl chloride resins, polypropylene resins, polyethylene resins, acrylic resins, resin plate composed mainly of ABS resin or the like, or they shall foamed) at least one can be cited such. These decorative board substrate may be used by laminating alone or in combination of two or more.
[0110]
　Here, the conifers, for example, fir, Japanese larch, spruce, cedar, cypress, pine, Sequoia, spruce, and the like. The hardwood, for example, lauan, Sina, birch, Sen, beech, oak, meranti, and the like. As the early Shigeki, poplar, Farukata, acacia, Kamerere, eucalyptus, Taminaria and the like.
[0111]
　Softwood plywood, hardwood plywood, fast Shigeki number of stacked wood veneer in the case of using a wood plywood plywood (number plies) is not limited, is preferably usually 3 to seven, 5-7 sheets are more preferable. The adhesive used during wood plywood manufactured is not limited, known woodworking adhesives can be widely used.
[0112]
　As the adhesive, for example, polyvinyl acetate, polyvinyl chloride, vinyl chloride - vinyl acetate copolymer, ethylene - acrylic acid copolymer, ionomer, butadiene - acrylonitrile rubber, neoprene rubber, the active ingredient of natural rubber adhesives and the like. Further, as the thermosetting adhesive, melamine, phenol, urea-based (vinyl acetate - urea, etc.) adhesives such as also exemplified.
[0113]
　The thickness of the decorative board base material is not limited, but is preferably about 2 ~ 15 mm, about 2 ~ 12 mm is more preferable.
[0114]
　Lamination method for laminating the decorative sheet and decorative laminate substrate may be adopted a method in which affixing each by but is not limited to, for example, an adhesive. The adhesive may be suitably selected from known adhesive according to the type of the decorative board base material. For example, polyvinyl acetate, polyvinyl chloride, vinyl chloride - vinyl acetate copolymer, ethylene - acrylic acid copolymer, ionomer, urethane-based reactive hot-melt (. Hereinafter referred to as "PUR-based adhesive") reactions, such as or type hot melt adhesive or the like, butadiene - acrylonitrile rubber, neoprene rubber, natural rubber, and the like. These adhesives are used alone or in combination of two or more thereof.
[0115]
　Aforementioned decorative sheet of the present invention has both a superior bending workability and scratch resistance even in high load conditions, it is useful as a cosmetic material.
Example
[0116]
　Next, the present invention embodiment will be described in more detail, the present invention is not intended to be limited by these examples.
[0117]
　The decorative sheet obtained in each example was evaluated the properties or characteristics by the following measurement method.
(1) indentation hardness (H IT )
　by the method described in the specification text, indentation hardness H of the surface protective layer IT 1 , indentation hardness H of the second olefin resin layer IT 2 and indentation hardness H of the first olefin resin layer we 3 were measured.
(2) Scratch resistance test (coin scratch test)
　The decorative sheet prepared in Examples and Comparative Examples, density fiberboard in a thickness of 2.5 mm (MDF; decorative board base material) a water-soluble emulsion adhesive onto to prepare a decorative plate by bonding through. Incidentally, the water-soluble emulsion-based adhesives, the following were used.
Water-soluble emulsion-based adhesive
main agent: "BA-10L" Japan Coating Resins Co., modified ethylene-vinyl acetate
curing agent: "BA-11B" Japan Coating Resins Co., isocyanate-based
blending ratio main agent: curing agent = 100: 2.5 (weight ratio)　
　The decorative plate were used to evaluate the scratch resistance by the coin scratch test. Specifically, two 10-yen coins tilted at 45 ° into contact with the test piece decorative sheet surface (the surface protective layer side), and dragged in the horizontal direction while applying a load (4 kg load, 6 kg load and 7kg load) It was to evaluate the scratch state at the time. Evaluation criteria are as follows, both B rating higher (i.e., A or B) it is the pass.

A: 7kg not observed scratches in load
B: The scratches are observed in the 7kg load, not observed scratches in 6kg load
C: not observed flaws in 4kg load, scratches at 6kg load observed is
(3) bending property
　was evaluated bending property of the decorative sheet prepared in examples and Comparative examples. More specifically, when the wound such that the first olefin layer of the decorative sheet to a metal rod having a diameter of 3mm in contact, was evaluated for the presence or absence of cracks in the surface protective layer. The evaluation criteria are as follows.

A: cracks not visible
B: The microcracks Careful observation is slightly visible, range no performance problem
C: cracks clearly visible
(4) Impact resistance (Du Pont impact test )
　the impact resistance of the decorative laminates produced in examples and Comparative examples were evaluated using a DuPont impact tester (in accordance with JIS K5600-5-3). Specifically, it was evaluated whether to drop the weight prescribed weight from a height of 100mm to the decorative sheet surface veneer cracks in the decorative sheet occurs. The evaluation criteria are as follows.
A: No cracks visible
B: visible minute cracks with careful observation
C: cracks clearly visible can
(5) Stain resistance after Dupont impact test
　for decorative sheets prepared in Examples and Comparative Examples, the following It was evaluated stain resistance in the way.
(4) Oily black marker to test implement portion (manufactured by Teranishi Chemical Industry Co., Ltd.) was applied for, was visually evaluated residual degree of black Magic after wiped with a solvent (ethanol) immediately. The evaluation criteria are as follows.
A: Contamination remains invisible
B: very small contamination remaining Careful observation visible
C: visible clearly contaminated
　 Example 1
　first olefin resin layer 3, the second olefin resin layer 2, and a surface protective layer 1 There was fabricated a decorative sheet 10 which are laminated in this order.
[0118]
　First, the first olefin resin layer 3 made of a polyethylene sheet having a thickness of 80 [mu] m, and a second olefin resin layer 2 obtained by the following manufacturing method, were laminated through an adhesive layer.
[0119]
　Then, on the second olefin resin layer 2, the thickness after drying was coated so as to be 15μm by a roll coating method of the surface protective layer coating solution A having the following composition.
[0120]
　Then, using an electron beam irradiation device in the following environments oxygen concentration 200 ppm, an acceleration voltage 175KeV, to form a surface protective layer 1 is cured by irradiating an electron beam under conditions of 5 Mrad.
[0121]
　Furthermore, by embossing by heat and pressure from the surface protective layer 1 side, to prepare a decorative sheet of Example 1 to form an uneven pattern of the wood grain conduit pattern.

　isotactic pentad fraction of 97.8%, MFR is 15g / 10min (230 ℃), highly crystalline homopolymers of molecular weight distribution (Mw / Mn) 2.3 a polypropylene resin, a nucleating agent 2,2'-methylenebis (4,6-di-tert-butylphenyl) by extruding a melt extruder which was added sodium phosphonate 1000 ppm, a thickness of 80μm crystallites It was formed a polypropylene sheet consisting of homopolymer polypropylene.

- 2-functional urethane acrylate oligomer 80 parts by mass
(polyol component polyester diols, glass transition point: 25 ° C., molecular weight 1500)
, hexafunctional aliphatic urethane acrylate oligomer 20 parts by mass
(a glass transition point : 200 ° C. or higher, molecular weight 1500, manufactured by Kyoeisha chemical Co., Ltd. UA306H)
· inorganic fine particles 14 parts by mass
(silica fine particles) having an average particle size of 10μm
　 example 2
　formulation of hexafunctional aliphatic urethane acrylate oligomer of the surface protective layer coating solution a change the amount of 100 parts by weight, except that no blending difunctional urethane acrylate oligomer, in the same manner as in example 1, to prepare a decorative sheet of example 2.
[0122]
　 Example 3
　20 parts by mass the amount of the difunctional urethane acrylate oligomer of the surface protective layer coating liquid A, except for changing the amount of hexafunctional aliphatic urethane acrylate oligomer 80 parts by mass, in the same manner as in Example 1 Te, to prepare a decorative sheet of example 3.
[0123]
　 Example 4
　as the second olefin resin layer 2 of Example 1, except that the 2000ppm the addition amount of the nucleating agent in the same manner as in Example 1, to prepare a decorative sheet of Example 4.
[0124]
　 Example 5
　20 parts by weight the amount of the difunctional urethane acrylate oligomer of the surface protective layer coating liquid A, to change the amount of hexafunctional aliphatic urethane acrylate oligomer 80 parts by mass, further addition of nucleating agents except for using 2000ppm in the same manner as in example 1, to prepare a decorative sheet of example 5.
[0125]
　 Comparative Example 1
　as the second olefin resin layer 2 of Example 1, a melt extruder without the addition of a nucleating agent 2,2'-methylenebis (4,6-di-tert-butylphenyl) sodium phosphonate 1000ppm except for using the extruded polypropylene sheet in the same manner as in example 1, to prepare a decorative sheet of Comparative example 1.
[0126]
　 Comparative Example 2
　as the second olefin resin layer 2 of Example 3, a melt extruder without the addition of a nucleating agent 2,2'-methylenebis (4,6-di-tert-butylphenyl) sodium phosphonate 1000ppm except for using the extruded polypropylene sheet in the same manner as in example 3, to prepare a decorative sheet of Comparative example 2.
[0127]
[Table 1]

[0128]
　From the results of Table 1, the decorative sheet of Example 1-5 is excellent in abrasion resistance under high load conditions, it can be confirmed to have excellent bending workability. Further, by comparing the Examples 1-3 and Examples 4-5, the second olefin resin layer 2 of the indentation hardness H IT 2 by setting to less than or more 100 MPa 140 MPa (preferably 130MPa or less) , excellent scratch resistance and bending in addition to workability can be confirmed to obtain a DuPont impact resistance and also superior effect in terms of stain resistance after Dupont impact.
Industrial Applicability
[0129]
　Decorative sheet of the present invention is excellent in abrasion resistance under high load conditions, has excellent bending workability, the surface material of building materials, in particular can be used as a floor for the decorative material.
DESCRIPTION OF SYMBOLS
[0130]
1 surface protection layer
2 second olefin resin layer
3 first olefin resin layer
4 recesses (embossed
recesses) 10 decorative sheet
11 veneer substrate
12 veneer
20 measured sample
21 Berkovich indenter
22 direction to apply a load

The scope of the claims
[Requested item 1]The first olefin resin layer, the second olefin resin layer, and the decorative sheet having a surface protective layer in this order,
　the second olefin resin layer indentation hardness H of IT 2 of the surface protective layer indentation hardness H IT 1 ; and the following formulas (1) and　
　(2) H iT 2　≧ 100 MPa (1)
H　iT 1 > H iT　　　　 　2 (2) decorative sheet characterized by satisfying.
[Requested item 2]
　Indentation hardness H of the surface protective layer IT 1 is the following formula
　(3); 450 MPa> H IT 1　　(3)
meet, decorative sheet according to claim 1.
[Requested item 3]
　The second olefin resin layer indentation hardness H of IT 2 and the indentation hardness of the first olefin resin layer H IT 3 and the following formula (4);
　H IT 2 > H IT　　　　　3 (4) meet, decorative sheet according to claim 1 or 2.
[Requested item 4]
　The second olefin resin layer is microcrystalline olefin resin layer, the decorative sheet according to any one of claims 1 to 3.
[Requested item 5]
　The surface protective layer contains the following inorganic fine particles having a mean particle size of 20 [mu] m, the decorative sheet according to any one of claims 1 to 4.
[Requested item 6]
　In order in the thickness direction, and the decorative board base material, veneer consists laminate and a decorative sheet according to any one of claims 1 to 5.