JP6507473B2 - Cosmetic sheet - Google Patents

Description

  The present invention relates to a decorative sheet useful as a decorative sheet for flooring.

  Conventionally, in order to improve the impact resistance and caster resistance of the decorative sheet for floorings, a method is known in which the thickness of the entire decorative sheet is increased. When such a decorative sheet is too thick, the emboss shapeability becomes sweet, the roll becomes thick, and the curling of the roll becomes strong, so that roll lamination can not be performed. There is.

  As a decorative sheet for floor material which solved the above-mentioned problem, a decorative sheet which has a backer layer on the back side of a decorative sheet is proposed (for example, refer to patent documents 1).

  However, since it is necessary to provide a backer layer on the back surface side of the above-mentioned decorative sheet, there is a problem that manufacturing cost becomes expensive and process loss in manufacturing occurs. When the backer layer is formed by extruding a molten resin, the emboss shape on the surface of the decorative sheet disappears because the molten resin is at a high temperature, and therefore the emboss shape is inferior and the emboss shape remaining without disappearance is also practically used It has a problem that it is easy to disappear in the case of the above, and is inferior in embossing fastness.

  As a method of solving the above-mentioned problem, although the method of thickening the thickness of the substrate sheet without providing the backer layer is used, if the thickness of the substrate sheet is too thick, the thickness of the whole decorative sheet becomes thick. The problem arises when the thickness of the entire decorative sheet described above is increased.

  Moreover, although the method of thickening the thickness of the transparent resin layer without providing a backer layer is used, when the thickness of the transparent resin layer is too thick, the heat absorption is insufficient in the embossing process, and the embossing shapeability and embossing are not sufficient. There is a problem that the fastness is lowered, and the substrate sheet is warped or broken due to the thermal contraction after the floor material processing.

  Therefore, it is not necessary to have a backer layer, and it is excellent in impact resistance, caster resistance, emboss shapeability and emboss fastness required for decorative sheets for floorings, and is a flooring material for which warping due to heat shrinkage is suppressed. Development of a sheet is desired.

2007-98855 gazette

  An object of the present invention is to provide a decorative sheet useful as a decorative sheet for flooring, which is excellent in impact resistance, caster resistance, emboss shapeability and emboss fastness, and warpage due to heat shrinkage is suppressed. I assume.

  As a result of intensive studies, the present inventors found that in the decorative sheet for floor material having at least the transparent resin layer on the substrate sheet, the thickness ratio of the thickness of the substrate sheet to the thickness of the transparent resin layer It has been found that the above object can be achieved by setting the total of the thickness of the transparent resin layer and the thickness of the base sheet to a specific range, and achieving the present invention.

That is, the present invention relates to the following decorative sheet.
1. A decorative sheet having at least a transparent resin layer on a substrate sheet, wherein (1) the thickness ratio (t1) of the thickness (t1) of the transparent resin layer to the thickness (t2) of the substrate sheet / (T2) is 1.5 / 1.0 to 1.0 / 1.5, and (2) the sum (t1) of the thickness (t1) of the transparent resin layer and the thickness (t2) of the substrate sheet ) + (T2) is 300 to 600 μm,
A cosmetic sheet characterized by
2. The decorative sheet according to Item 1, wherein the transparent resin layer has a thickness of 150 μm or more.
3. The decorative sheet according to Item 1 or 2, wherein the transparent resin layer is an olefin resin layer.
4. The decorative sheet according to any one of Items 1 to 3, wherein the base sheet contains at least one of a polyolefin resin and a polyester resin.
5. The decorative sheet according to any one of Items 1 to 4, further having a pattern-patterned layer between the base sheet and the transparent resin layer.
6. The decorative sheet according to any one of Items 1 to 5, wherein a surface protective layer is laminated on the transparent resin layer.
7. 7. The decorative sheet according to item 6, wherein the surface protective layer is an ionizing radiation curable resin layer.
8. 8. The decorative sheet according to item 6 or 7, further comprising a primer layer between the transparent resin layer and the surface protective layer.
9. 9. The decorative sheet according to any one of items 1 to 8, which is embossed from the side of the transparent resin layer.
10. 10. A decorative sheet according to any one of the above items 1 to 9, which is for flooring.
11. The decorative board formed by laminating the decorative sheet in any one of said claim | item 1-10 on a covering material.

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

  The decorative sheet for flooring of the present invention has at least a transparent resin layer and a surface protective layer in this order on a substrate sheet, and (1) the thickness (t1) of the transparent resin layer and the thickness of the substrate sheet Thickness ratio (t1) / (t2) to (t2) is 1.5 / 1.0 to 1.0 / 1.5, (2) thickness (t1) of the transparent resin layer and the substrate A total (t1) + (t2) with the thickness (t2) of the sheet is 300 to 600 μm.

  In the decorative sheet for floor materials of the present invention having the above characteristics, the total of the thickness of the transparent resin layer and the thickness of the base sheet is within a specific range, and the thickness ratio of the transparent resin layer to the base sheet is Since it is a suitable range, it is excellent in impact resistance and caster resistance. For this reason, a backer layer is not required, and combined with the thickness ratio and the total thickness being in a specific range, the emboss shape and the emboss fastness are excellent.

  Furthermore, by defining the thickness ratio and the sum of the thicknesses, the thickness of the transparent resin layer is not too large, and warpage due to thermal contraction of the decorative sheet for flooring is suppressed.

  In the decorative sheet for flooring of the present invention, the total (t1) + (t2) of the thickness (t1) of the transparent resin layer and the thickness (t2) of the base sheet is 300 to 600 μm. When (t1) + (t2) is less than 300 μm, the impact resistance and the caster resistance are inferior. Moreover, when (t1) + (t2) exceeds 600 micrometers, it is inferior to embossing shaping property and embossing fastness. 300-500 micrometers is preferable and, as for (t1) + (t2), 300-400 micrometers is more preferable. When (t1) + (t2) is too thick, there is a possibility that winding deviation may occur when forming a roll, and roll formation may become difficult.

  The decorative sheet for flooring of the present invention has a thickness ratio (t1) / (t2) of the thickness (t1) of the transparent resin layer to the thickness (t2) of the substrate sheet of 1.5 / 1.0 to 1. It is 0 / 1.5. If (t1) / (t2) is smaller than 1.0 / 1.5, the thickness of the transparent resin layer becomes thin, so the impact resistance is inferior. In addition, if (t1) / (t2) is smaller than 1.0 / 1.5, the abrasion resistance is inferior and the sense of depth of the handle is also reduced.

  In addition, if (t1) / (t2) is greater than 1.5 / 1.0, the thickness of the transparent resin layer becomes thick, so the heat absorption is insufficient in the embossing step, and the embossing shapeability and the embossing fastness are poor. . In addition, when the thickness of the transparent resin layer is increased, the amount of warpage due to the thermal contraction of the transparent resin layer is increased, so the amount of warpage of the decorative sheet for floor material is also increased.

The condition that (t1) / (t2) is less than 1.0 / 1.5 means that the thickness ratio (t1) / (t2) is less than 1.0 / 1.5. The ratio is small, indicating that the ratio of (t2) is large. In addition, when (t1) / (t2) is greater than 1.5 / 1.0, the ratio of (t1) is greater than when the thickness ratio (t1) / (t2) is 1.5 / 1.0. Indicates that the ratio of (t2) is small. Hereinafter, the same applies in the present specification.
The thickness ratio (t1) / (t2) is preferably 1.2 / 1.0 to 1.0 / 1.0.

(Base sheet)
The base sheet is not limited, but is preferably a base sheet containing a polyolefin resin as a resin component. A sheet substantially consisting of a polyolefin resin is used.

  The polyolefin resin is not particularly limited, and those generally used in the field of decorative sheets can be used. For example, polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-propylene-butene copolymer, polyolefin-based thermoplastic elastomer, etc. Can be mentioned. Among these, polypropylene and polyolefin thermoplastic elastomer are particularly preferable.

  Also preferred is a homopolymer or copolymer containing polypropylene as a main component, for example, homopolypropylene resin, random polypropylene resin, block polypropylene resin, and polypropylene crystal parts and having 2 to 20 carbon atoms other than propylene. -Include olefins. Other than these, a propylene-α-olefin copolymer containing 15 mol% or more of ethylene, butene-1, 4-methylpentene-1, hexene-1 or octene-1 is also preferable.

  The polyolefin-based thermoplastic elastomer is preferably a mixture of hard segment with isotactic polypropylene and soft segment with atactic polypropylene in a weight ratio of 80:20.

  The polyolefin resin may be formed into a film by, for example, a calender method, an inflation method, a T-die extrusion method or the like.

  The substrate sheet may also be a substrate sheet containing a polyester resin as a resin component. In this case, a sheet substantially made of polyester resin is used.

  The polyester resin is not particularly limited, and those generally used in the field of decorative sheets can be used. For example, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN) and the like can be mentioned. Among these, polybutylene terephthalate is particularly preferred.

  In addition, the base sheet may contain at least one of a polyolefin resin and a polyester resin. In addition, when a base material sheet contains a polyolefin resin and a polyester resin, the base material sheet which consists of one layer may be formed of resin which mixed polyolefin resin and polyester resin, and the base material which consists of a plurality of layers The sheet may be formed by laminating a sheet containing a polyolefin resin and a sheet containing a polyester resin.

  In addition, the substrate sheet may be formed by laminating a plurality of layers containing a polyolefin resin. In this case, the respective layers forming the substrate sheet may differ in the type and amount of the contained polyolefin resin, and may differ in the type and the amount of the additive. As an example of such a substrate sheet, for example, (i) a substrate sheet in which a plurality of layers having different blending ratios of a block copolymer of a polyolefin and a random copolymer in a layer are laminated, (ii) a pigment And a base sheet obtained by laminating a layer containing a filler and the like and a layer not containing the same, and a base sheet obtained by laminating a plurality of layers having different amounts of the pigment, filler and the like in the layer (iii).

Similarly, the substrate sheet may be formed by laminating a plurality of layers containing a polyester resin. Also in this case, the respective layers forming the substrate sheet may differ in the type and amount of the polyester resin used, and in the type and the amount of the additive.
The configuration of these substrate sheets may be appropriately selected according to the thickness, hardness, etc. of the adherend such as a wood substrate used when laminating the decorative sheet on the adherend to form a decorative board. .

  The thickness of the substrate sheet is not particularly limited and can be set according to the product characteristics, but is preferably about 150 to 300 μm, more preferably about 160 to 240 μm, and still more preferably about 180 to 200 μm.

  An additive may be mix | blended with a base material sheet as needed. Examples of the additive include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, colorants (see below) and the like. The compounding amount of the additive can be appropriately set according to the product characteristics.

  The colorant is not particularly limited, and known colorants such as pigments and dyes can be used. For example, inorganic pigments such as titanium white, zinc flower, red iron oxide, ultramarine blue, cobalt blue, titanium yellow, yellow lead, carbon black, etc. isoindolinone, Hansa yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indaslen Organic pigments (including dyes) such as Blue RS and aniline black; metallic pigments such as aluminum and brass; and pearlescent pigments composed of titanium dioxide-coated mica and foil powders such as basic lead carbonate.

  If necessary, one surface or both surfaces of the substrate sheet may be subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, and dichromic acid treatment. For example, when performing corona discharge treatment, the surface tension of the substrate sheet surface may be 30 dyne or more, preferably 40 dyne or more. The surface treatment may be performed according to the usual method of each treatment.

  If necessary, a primer layer may be provided on one side or both sides of the substrate sheet.

  The primer layer can be formed by applying a known primer agent to one side or both sides of the substrate sheet. As a primer agent, for example, a urethane resin based primer agent composed of an acrylic modified urethane resin, a primer agent composed of a urethane-cellulose based resin (for example, a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton) Can be mentioned.

Although the application amount of the primer agent is not particularly limited, it is usually about 0.1 to ²⁰ g / m ² , preferably about 0.5 to 10 g / m ² .

(Transparent resin layer)
The transparent resin layer may be colored as long as it is transparent, or may be translucent within the range in which the design pattern layer can be visually recognized.

  Examples of the resin forming the transparent resin layer include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid Ester copolymers, ionomers, polymethylpentenes, acrylic esters, methacrylic esters, polycarbonates, cellulose triacetate and the like can be mentioned. Among the above, polyolefin resins such as polypropylene are preferable. More preferably, it is a polyolefin resin having stereoregularity. When using polyolefin resin, it is desirable to form a transparent resin layer by the extrusion method of molten polyolefin resin.

  In the transparent resin layer, if necessary, a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a radical scavenger, a soft component Various additives such as (for example, rubber) may be included.

  The thickness of the transparent resin layer is not particularly limited, but is preferably 150 μm or more. By setting the thickness of the transparent resin layer to 150 μm, when the design pattern layer is laminated on the lower layer, the sense of depth of the design is increased, the designability is improved, and the abrasion resistance of the decorative sheet for floor material is improves. The thickness of the transparent resin layer is preferably about 150 to 300 μm, more preferably about 160 to 240 μm, and still more preferably about 200 to 220 μm. If the thickness is too thin, impact resistance and caster resistance may be poor. If the thickness is too thick, there is a possibility that the embossing shapeability and the emboss fastness may be inferior, and the amount of warping due to the thermal contraction of the transparent resin layer may be large, and the amount of warping of the decorative sheet for flooring following this. There is also a risk that

  If necessary, the surface of the transparent resin layer, which is to be the surface protective layer, is subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, and dichromic acid treatment. It is also good. The surface treatment may be performed according to the usual method of each treatment.

  The layer structure of the decorative sheet for flooring of the present invention is not particularly limited as long as it has the above-mentioned base sheet and transparent resin layer, but for example, a pattern-patterned layer, transparency on the base sheet It is preferable that the resin layer and the surface protective layer be sequentially laminated. Moreover, the layer structure which laminates | stacks a design pattern layer, an adhesive bond layer, a transparency resin layer, a primer layer, and a surface protective layer in order on a base material sheet is also suitable.

  Hereinafter, as a specific layer structure, the above layer structure will be exemplified, and layers other than the surface protective layer will be described.

(Pattern pattern layer)
A picture pattern layer can be formed on the base sheet. The design pattern layer gives the decorative sheet for floor material a design with a desired design, and the type of design etc. is not particularly limited. For example, grain patterns, grain patterns, grain patterns, tile patterns, brick pile patterns, grain patterns, skin patterns, geometric figures, characters, symbols, abstract patterns and the like can be mentioned.

  The method of forming the pattern layer is not particularly limited. For example, colored ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) together with a binder resin in a solvent (or dispersion medium), coating It may be formed by a printing method using an agent or the like.

  Examples of coloring agents include inorganic pigments such as carbon black, titanium white, zinc flower, red iron oxide, red iron oxide, azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments And organic pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxychloride; fluorescent pigments; nightlight pigments and the like. These colorants can be used alone or in combination of two or more. In these colorants, fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like may be further blended.

  As the binder resin, for example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum Examples thereof include system resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, cellulose derivatives, rubber resins and the like. These resins may be used alone or in combination of two or more.

  Examples of the solvent (or dispersion medium) include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane and methylcyclohexane; ethyl acetate, butyl acetate, acetic acid-2-methoxyethyl, acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol and propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone Organic solvents; Ether solvents such as diethyl ether, dioxane, tetrahydrofuran, etc .; Dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene Inorganic solvents and the like, such as water; chlorinated organic solvents. These solvents (or dispersion media) can be used alone or in combination of two or more.

  As a printing method used for formation of a picture pattern layer, a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, an inkjet printing method etc. are mentioned, for example. In the case of forming a solid patterned pattern layer, for example, a roll coating method, a knife coating method, an air knife coating method, a die coating method, a lip coating method, a comma coating method, a kiss coating method, a flow coating method, dip Various coating methods such as a coating method can be mentioned. In addition, the hand-painting method, the ink flow method, the photography method, the transfer method, the laser beam drawing method, the electron beam drawing method, the partial vapor deposition method such as metal, the etching method, etc. Good.

  The thickness of the pattern layer is not particularly limited and may be appropriately set according to the product characteristics, but the layer thickness after drying is about 0.1 to 20 μm.

(Primer layer)
A primer layer may be provided on the transparent resin layer to facilitate formation of the surface protective layer.
The primer layer can be formed by applying a known primer agent to the transparent resin layer. As a primer agent, the urethane resin type primer agent which consists of an acryl modified urethane resin etc., the resin type primer agent which consists of a block copolymer of an acryl and a urethane etc. are mentioned, for example.

Although the application amount of the primer agent is not particularly limited, it is usually about 0.1 to ²⁰ g / m ² , preferably about 0.5 to 10 g / m ² .

(Surface protection layer)
In order to impart surface physical properties such as scratch resistance, abrasion resistance, water resistance, stain resistance and the like, a surface protective layer can be provided on the front surface of the decorative sheet for flooring. As a resin for forming the surface protective layer, a curable resin such as a thermosetting resin or an ionizing radiation curable resin is preferable. In particular, ionizing radiation curable resins are preferred from the viewpoint of high surface hardness, productivity and the like.

  As a thermosetting resin, for example, unsaturated polyester resin, polyurethane resin (including two-component curing polyurethane), epoxy resin, amino alkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, melamine -Urea co-condensation resin, silicone resin, polysiloxane resin etc. are mentioned.

A crosslinking agent, a curing agent such as a polymerization initiator, and a polymerization accelerator can be added to the resin.
For example, as a curing agent, isocyanate, organic sulfonate, etc. can be added to unsaturated polyester resin, polyurethane resin, etc., organic amine etc. can be added to epoxy resin, peroxides such as methyl ethyl ketone peroxide, azoisobutyl nitrile etc. Radical initiators can be added to the unsaturated polyester resin.

  As a method of forming a surface protection layer with thermosetting resin, the method of apply | coating the solution of thermosetting resin with coating methods, such as a roll-coating method and a gravure coat method, and drying and hardening is mentioned, for example. The application amount of the solution is about 5 to 30 μm, preferably about 10 to 20 μm, in terms of the solid content after drying the solution.

  The ionizing radiation curable resin is not limited as long as it is a resin that causes a crosslink polymerization reaction upon irradiation with ionizing radiation and changes to a three-dimensional polymer structure. For example, one or more of prepolymers, oligomers and monomers each having a polymerizable unsaturated bond or an epoxy group crosslinkable by irradiation of ionizing radiation can be used. For example, acrylate resins such as urethane acrylate, polyester acrylate and epoxy acrylate; silicon resins such as siloxane; polyester resins; epoxy resins and the like.

  Examples of ionizing radiation include visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light and the like), X-rays, electron beams, ion beams and the like. Among these, ultraviolet light and electron beams are preferable.

  As an ultraviolet light source, light sources of an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, and a metal halide lamp can be used. The wavelength of the ultraviolet light is about 190 to 380 nm.

  As the electron beam source, for example, various electron beam accelerators such as a Cockcroft Walt type, a bande graft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The energy of the electron beam is preferably about 100 to 1000 keV, and more preferably about 100 to 300 keV. The irradiation dose of the electron beam is preferably about 2 to 15 Mrad.

  The ionizing radiation curable resin is sufficiently cured by irradiation with an electron beam, but in the case of curing by irradiation with ultraviolet light, it is preferable to add a photopolymerization initiator (sensitizer).

  In the case of a resin system having a radically polymerizable unsaturated group, the photopolymerization initiator is, for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler's benzoyl benzoate, Michler's ketone, diphenyl sulfide, dibenzyl disulfide At least one of diethyl oxalate, triphenyl biimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used. In the case of a resin system having a cationically polymerizable functional group, for example, at least one of an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, and a freeoxysulfoxonium diallyiodosyl salt. Can be used.

  Although the addition amount of the photopolymerization initiator is not particularly limited, it is generally about 0.1 to 10 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.

  As a method of forming the surface protective layer from the ionizing radiation curable resin, for example, a solution of the ionizing radiation curable resin may be applied by a coating method such as a gravure coating method or a roll coating method. The application amount of the solution is about 5 to 30 μm, preferably about 10 to 20 μm, in terms of the solid content after drying the solution.

  The surface protective layer preferably contains a hard filler for the purpose of further improving the scratch resistance. The hard filler is not particularly limited as long as the scratch resistance of the surface protective layer can be further improved, but spherical inorganic fine particles are preferably used. Examples of the inorganic fine particles include powdered aluminum oxide, silicon carbide, silicon dioxide, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, and the like. Examples of such materials include diamond, sand of gold, glass fiber, fused silica and the like.

  As a specific example of the said hard filler, the spherical silica particle described in patent 4834999 can be illustrated, for example.

The pore volume of the hard filler is preferably less than 1.0 ml / g, and more preferably 0 ml / g or more and less than 1.0 ml / g. Moreover, the apparent specific gravity of the case hard filler is silica is greater than 0.4 g / cm ^2, is preferably 2.2 g / cm ² or less.

  The content of the hard filler is 1 to 10 parts by weight with respect to 100 parts by weight of the resin component forming the surface protective layer, which is a curable resin such as the thermosetting resin or the ionizing radiation curable resin. Is preferred.

  It is preferable that the average particle diameter of the said hard filler is 1-5 micrometers.

  The surface protective layer may optionally contain a matting agent. Although it does not specifically limit as said matting agent, For example, a silica is mentioned. As said silica, it is preferable that they are non-spherical particle | grains from the point which can fully exhibit the matting effect.

  As the matting agent, one having a pore volume of 1.8 to 3.0 ml / g, an apparent specific gravity of 0.05 to 0.22 g / ml and an oil absorption of 300 ml / 100 g or more is used. Is preferred. It is more preferable to use one having a pore volume of 1.9 to 2.5 ml / g, an apparent specific gravity of 0.10 to 0.20 g / ml, and an oil absorption of 300 to 400 ml / 100 g. By using the matting agent having a pore volume of 1.8 to 3.0 ml / g, the irregular reflection effect of light can be efficiently obtained, so that a good matting effect can be obtained.

  It is preferable that content of the said matting agent is 8-20 weight part with respect to 100 weight part of resin components which form a surface protective layer. Moreover, it is preferable that the average particle diameter of the said matting agent is 9-15 micrometers.

  The thickness of the surface protective layer is preferably 5 to 30 μm. When the thickness of the surface protective layer is smaller than 5 μm, the scratch resistance may be deteriorated. Moreover, when it is thicker than 30 μm, there is a possibility that the curling of the decorative sheet for flooring may easily occur. The thickness of the surface protective layer is more preferably 10 to 20 μm.

  The surface protective layer may optionally contain an ultraviolet light absorber, a light stabilizer, a plasticizer, a stabilizer, a filler, a dispersant, a colorant such as a dye or a pigment, a solvent, an antibacterial agent, etc. .

(Embossed)
The decorative sheet for floorings of the present invention may be embossed from the side of the transparent resin layer after the transparent resin layer is formed. Moreover, when a surface protective layer is formed on a transparent resin layer, after laminating | stacking the said surface protective layer on the said transparent resin layer, embossing may be given from the surface protective layer side. .

  The embossing method is not particularly limited, and for example, a method of heat-softening the front surface of the transparent resin layer or the surface protective layer, pressing and shaping by the embossing plate, and cooling is mentioned as a preferable method. For embossing, a known sheet-fed or rotary emboss machine is used. As an uneven | corrugated shape, there exist a wood-grain board conduit groove, a stone plate surface unevenness | corrugation (a granite cleavage surface etc.), cloth surface texture, a satin, a grain, a hairline, a line streak, etc., for example.

  The decorative sheet of the present invention can be made into a decorative board by laminating on an adherend. The adherend is not limited, and one similar to that used for a known decorative board can be used.

  Examples of the adherend include wood substrates, metals, ceramics, plastics, glass and the like. In particular, the decorative sheet of the present invention can be suitably used for a wood substrate. Wood base materials include veneers made of various materials such as cedar, rattan, rattan, pine, rattan, rattan, rattan, laan, teak, melapy, veneered wood, wood plywood, wood fiber board (MDF, HDF, etc. A hard chip board (particle board etc.), a soft chip board (cork etc.), or a composite substrate on which the chip board is laminated. Among the above-mentioned wood base materials, wood fiber boards, soft chip boards, or composite base materials on which soft chip boards are laminated are preferable, and wood fiber boards can be suitably used in view of cost and fastness. A flexible chip board or a composite substrate in which a soft chip board and a wood fiber board are laminated can be preferably used from the viewpoint of the warmth and the feeling of walking.

  The decorative sheet of the present invention has at least a transparent resin layer on a substrate sheet, and the thickness ratio (t1) / (t2) of the thickness (t1) of the transparent resin layer to the thickness (t2) of the substrate sheet Is 1.5 / 1.0 to 1.0 / 1.5, and the total (t1) + (t2) of the thickness (t1) of the transparent resin layer and the thickness (t2) of the substrate sheet is 300 to 500 Since it is 600 μm, it is excellent in impact resistance, caster resistance, emboss shapeability and emboss fastness, and warpage due to heat shrinkage is suppressed.

It is sectional drawing showing an example of the decorative sheet for floorings of this invention.

  Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples. However, the present invention is not limited to the examples.

(Preparation of decorative sheet for floor material)
Example 1
A colored polypropylene sheet (thickness 160 μm) was prepared as a substrate sheet. After applying corona discharge treatment to the surface and back surface of the above-mentioned base material sheet, a primer agent was applied to the surface and back surface, respectively, and a primer layer (each 2 micrometers in thickness) was formed. The primer agent is a mixture of 100 parts by weight of a resin composition and 5 parts by weight of hexamethylene diisocyanate (hardening agent), and the above resin composition is an acrylic urethane copolymer, an acrylic polyol, a triazine-based ultraviolet absorber (5 parts by mass %) As a mixture.

  Next, a patterned layer (thickness 2 μm) was formed on the surface primer layer, and a transparent adhesive layer (thickness 3 μm) was formed thereon. A transparent thermoplastic polypropylene resin was heat-melt extruded on a transparent adhesive layer with a T-die extruder to form a transparent resin layer (thickness 240 μm).

  Next, the surface of the transparent resin layer was subjected to corona discharge treatment, and a two-component curable urethane resin was applied to form a primer layer (2 μm in thickness) on the transparent resin layer.

  Subsequently, the composition for surface protective layer formation was coated by the thickness of 15 micrometers by the gravure coat method on the primer layer. The composition for forming a surface protective layer comprises 80 parts by weight of a bifunctional urethane acrylate oligomer as a resin component (weight average molecular weight 1500 glass transition temperature-55 ° C), and hexafunctional aliphatic urethane acrylate oligomer (weight average molecular weight 1500 glass transition temperature) 200 parts or more contained 20 parts by weight of UA 306H manufactured by Kyoeisha Chemical Co., Ltd. and contained 14 parts by weight of amorphous silica having an average particle diameter of 11 μm as a matting agent with respect to 100 parts by weight of the resin component.

  Subsequently, the coating film is crosslinked and cured by irradiating the coating film of the composition for forming a surface protective layer under the condition of an acceleration voltage of 175 keV and 5 Mrad (50 kGy) in an atmosphere with an oxygen concentration of 200 ppm. The surface protective layer was formed.

Finally, a decorative sheet for flooring was produced by embossing from the surface protective layer side under conditions of a sheet temperature of 140 ° C. and a pressure of 10 to 40 kg / cm ² . The thickness ratio (t1) / (t2) of the thickness (t1) of the transparent resin layer to the thickness (t2) of the base sheet is 1.5 / 1.0, and the total thickness (t1) + (t2) Was 400 μm.

Examples 2 to 7 and Comparative Examples 1 to 7
The thickness (t1) of the transparent resin layer, the thickness (t2) of the substrate sheet, the thickness ratio (t1) / (t2), the total thickness (t1) + (t2), and the resin forming the substrate sheet A decorative sheet for flooring of Examples 2 to 7 and Comparative Examples 1 to 7 was produced in the same manner as in Example 1 except that the number 1 was changed.

(Preparation of floor dressings)
Examples 1 to 7 and Comparative Examples 1 to 7
The decorative sheet for floor material is a water-based adhesive such that the back surface primer layer side of the decorative sheet for floor material of Examples 1 to 7 and Comparative Examples 1 to 7 produced as described above is in contact with the wood substrate (MDF) (BA-10L / BA-11B, manufactured by Chuo Rika Kogyo Co., Ltd., application amount 7 g / size angle) The floor decorative material of Examples 1 to 7 and Comparative Examples 1 to 7 by bonding to a wood substrate Was produced.

Example 8
A floor covering material of Example 8 was produced in the same manner as in Example 3 except that the wood base was changed to a cork material.

(Evaluation method)
Impact resistance (Dupont impact test)
In accordance with the Dupont impact test according to JIS K 5600, a shot type having a hemispherical tip with a radius of 6.3 mm is allowed to stand on the surface of the floor covering material prepared as described above, and a 500 g weight weight is placed on the above shot type. Was evaluated by dropping from a height of 30 cm. Evaluation was performed based on the following evaluation criteria by the amount of dents.

In addition, the following evaluation criteria are the references | standards set with reference to the amount of dents of a general color floor being 500-600 micrometers. Here, with a general color floor, a veneer (0.25 mm in thickness) is laminated on plywood (11.8 mm in thickness), and UV coating (0.02 in thickness) is further applied on the veneer. It means the color floor being done.
:: 300 μm or less ○: more than 300 μm, 500 μm or less Δ: more than 500 μm, 600 μm or less ×: more than 600 μm

Castor-resistant floor fatigue tester No. It evaluated using 159-S Yasuda Seiki Seisakusho. Specifically, the floor decorative material prepared as described above was cut into a size of 5 cm × 20 cm to make a sample, and the sample was fixed on a fixing table. A weight of 15 kg was placed on the loading section, and one caster was brought into contact with the surface of the floor covering with the adjustment handle (total load 25 kg), and the caster fixed stand was operated to reciprocate 25000 at a speed of 10 m / min. . Evaluation was performed based on the following evaluation criteria by the amount of dents.
:: 50 μm or less ○: Over 50 μm, 80 μm or less Δ: Over 80 μm, 100 μm or less ×: Over 100 μm, 120 μm or less ××: Over 120 μm

The gloss value of the outermost surface of the decorative sheet for emboss formable floor material was measured. The gloss value was measured using a gloss meter PG-3D manufactured by Nippon Denshoku Kogyo Co., Ltd. The measurement of gloss value and G, as the reference value G ₀ of the measured value of the decorative sheet for floor material of Comparative Example 1 was evaluated according to the following evaluation criteria. In addition, the embossing plate used for embossing used the same thing in each Example and comparative example, and made the embossing speed the same speed.
◎: G is in the range of _{G 0 ± G 0 × 10%} ○: G is _{G 0} out of the scope of ± _{G 0} × 10%, in the range of from _{G 0} ± _{G 0} × 20% ×: G is out of the range of G ₀ ± G ₀ × 20%

Embossed Fastness The gloss value of the outermost surface of each decorative sheet for flooring was measured. Then, after making each flooring decorative sheet soak in glycerol heated to 130 ° C. for 30 seconds, the gloss value of the outermost surface of the decorative sheet for flooring was measured again. For measurement of the gloss value, a gloss meter PG-3D manufactured by Nippon Denshoku Kogyo Co., Ltd. was used. Evaluation criteria were as follows. In the following evaluation criteria, the gloss value of the decorative sheet before immersion and G _B, the gloss value of the decorative sheet after immersion and G _A. As G _A is the closer and G _B, it can be said that the excellent embossed fastness since the disappearance of the uneven pattern is small.
◎: G _A is in the range of G _B ± G _B × 10% :: G _A is outside the range of G _B ± G _B × 10% and in the range of G _B ± G _B × 20% △: G _A is outside the range of G _B ± G _B × 20%, and is within the range of G _B ± G _B × 30% ×: G _A is G _B ± G _B × 30% Out of range

A decorative sheet for flooring was attached to the surface of warped MDF due to heat contraction to prepare a floor decorative material of 1 × 6 size (width 313 mm × length 1840 mm). After subjecting the obtained floor decorative material to a test of performing 10 cycles of one cycle of leaving at 80 ° C. for 2 hours and then leaving at −20 ° C. for one cycle, the warp amount of the floor decorative material is It was measured. Evaluation criteria were as follows.
Good: Warpage amount of 1840 mm in the side direction is 5 mm or less Δ: Warpage amount of 1840 mm in the side direction exceeds 5 mm, 10 mm or less ×: Warpage amount of 1840 mm in the side direction exceeds 10 mm, 20 mm or less ××: Warpage of side length 1840 mm exceeds 20 mm

The contrast observation by visual observation was performed on the basis of the depth feeling of the decorative sheet having a thickness of 200 μm for the thickness- sensitive transparent resin layer of the handle, and the evaluation was made according to the following evaluation criteria.
:: Better sense of depth than standard ○: With sense of depth equivalent to standard △: Less sense of depth than standard

Rolled test It was investigated whether winding of the decorative sheet for flooring prepared was possible. Evaluation criteria were as follows.
In addition, in the following evaluation criteria, if the winding shift width at the time of rolling was less than 3 cm, it was possible to wind, and if the winding shift width was larger than 3 cm, it was not possible to roll.
○: Roll gap width 0 cm
:: Roll shift width exceeds 0 cm, within 3 cm, roll is possible ×: Roll shift width is over 3 cm, roll is not possible

Tests were carried out in accordance with the abrasion resistance JAS flooring wear A test. Specifically, a Taber abrasion tester was used on the floor decorative material manufactured as described above, and the number of rotations when the handle of each floor decorative material began to be taken was measured. Evaluation criteria were as follows. In addition, in the said test, rotation was performed on the conditions of grinding paper S-42 and load 1000g (one-wheel load 500gx2 piece, the load of a rubber disk is included).
:: The rotation speed when the handle starts to be taken is more than 2000 times ○: The rotation speed when the handle starts being taken is more than 1,500 times and less than 2000 times Δ: the handle is started to be taken The number of rotations is more than 1000 times and less than or equal to 1,500 times x: The number of rotations when the pattern starts to be taken is more than 500 times and less than or equal to 1000 times xx: the number of rotations when the pattern starts to be picked is 500 Less than

Walking feeling The walking on the floor covering prepared according to Examples 3 and 8 was evaluated for ease of walking (the reaction of the floor material to a person with stepping on the floor) by comparison with a common veneer floor. The evaluation was conducted by 10 randomly selected people.
In addition, with a common veneer floor, a veneer (0.30 mm thick) is laminated on plywood (11.6 mm thick) and UV coating (0.05 mm thickness) is applied on the veneer. Means a raised floor.
○: More than 8 people who felt that it was easier to walk than the veneer floor △: More than 6 people who felt that it was easier to walk than the veneer floor

  As apparent from the results of Table 1, the thickness ratio (t1) / (t2) of the thickness (t1) of the transparent resin layer to the thickness (t2) of the base sheet is 1.5 / 1.0 to 1. Example within the range of 0 / 1.5, where the sum (t1) + (t2) of the thickness (t1) of the transparent resin layer and the thickness (t2) of the base sheet is in the range of 300 to 600 μm The decorative sheets for floor materials of 1 to 7 were excellent in impact resistance, caster resistance, emboss shapeability and emboss fastness, and warpage due to heat shrinkage was suppressed.

  Furthermore, since the thickness of the transparent resin layer laminated | stacked on the design pattern layer is appropriate, the decorative sheet for floorings of Examples 1-7 increases the sense of depth of a handle, and is excellent in the designability, and The abrasion resistance was also excellent. Moreover, since (t1) + (t2) is an appropriate range, excellent results were shown in the roll forming test, and it was found that roll forming is possible in the roll forming process.

  On the other hand, in Comparative Example 1 in which (t1) + (t2) is as thin as 250 μm, the caster resistance is inferior, and in Comparative example 2 as thick as 700 μm, the embossing is inferior in shapeability and rolling is also difficult. I understand.

  The thickness ratio (t1) / (t2) of the thickness (t1) of the transparent resin layer to the thickness (t2) of the base sheet In Comparative Examples 3 to 5 in which the ratio of (t1) is large, the thickness of the transparent resin layer is Since it is too much, the curvature amount by heat contraction was large. In particular, in Comparative Example 3 in which the ratio of (t1) was large, the embossing shapeability and the embossing fastness were also inferior. Moreover, in Comparative Example 6 in which the ratio of (t2) is large, the thickness of the substrate sheet is too thick, so the transparent resin layer becomes relatively thin and the impact resistance is inferior.

  In Comparative Example 7 in which (t1) + (t2) is as thick as 700 μm and the ratio of (t1) is large at the thickness ratio (t1) / (t2), although the impact resistance and the caster resistance are excellent, the embossed shape is formed. It was found that the film was inferior in hardness and emboss fastness, the amount of warpage due to heat shrinkage was large, and roll formation was also difficult.

1. Primer layer Base sheet 3. Pattern layer 4. Transparent adhesive layer5. Transparent resin layer 6. Primer layer7. Surface protection layer

Claims (9)

A decorative sheet having at least a transparent resin layer on a substrate sheet,
(1) The thickness ratio (t1) / (t2) of the thickness (t1) of the transparent resin layer to the thickness (t2) of the base sheet is 1.0 / 1.0 to 1.0 / 1.5 And
(2) The total (t1) + (t2) of the thickness (t1) of the transparent resin layer and the thickness (t2) of the base sheet is 300 to 600 μm,
(3) The transparent resin layer is a transparent thermoplastic polypropylene resin layer ,
(4) The base sheet contains a polypropylene resin ,
A cosmetic sheet characterized by   The decorative sheet according to claim 1, wherein the transparent resin layer has a thickness of 150 μm or more. Between the transparent resin layer and the base sheet further comprises a picture pattern layer, the decorative sheet according to claim 1 or 2. The decorative sheet according to any one of claims 1 to 3 , wherein a surface protective layer is laminated on the transparent resin layer. The decorative sheet according to claim 4 , wherein the surface protective layer is an ionizing radiation curable resin layer. The decorative sheet according to claim 4 or 5 , further comprising a primer layer between the transparent resin layer and the surface protective layer. The decorative sheet according to any one of claims 1 to 6 , which is embossed from the side of the transparent resin layer. The decorative sheet according to any one of claims 1 to 7 , which is for flooring. A decorative board formed by laminating the decorative sheet according to any one of claims 1 to 8 on an adherend.

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